ORCID Profile
0000-0003-1136-2296
Current Organisations
University of Western Australia
,
University of Iowa
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Research Topics
In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Top 5 Research Topics
ANZSRC Field of Research (FoR)
Molecular and Organic Electronics | Nanotechnology | Organometallic Chemistry | Transition Metal Chemistry | Structural Chemistry and Spectroscopy | Other Chemical Sciences | Biochemistry and cell biology | Physical Chemistry of Materials | Organic Chemistry | Natural Products Chemistry | Synthetic biology | Electrochemistry | Organic Chemical Synthesis | Chemical Characterisation of Materials | Physical Chemistry (Incl. Structural) | Environmental biotechnology not elsewhere classified | Electrochemistry | Nanoscale Characterisation | Organometallic Chemistry | Photonic and electro-optical devices sensors and systems (excl. communications) | Electronics sensors and digital hardware | Electronic device and system performance evaluation testing and simulation
ANZSRC Socio-Economic Objective (SEO)
Expanding Knowledge in the Chemical Sciences | Expanding Knowledge in the Physical Sciences | Expanding Knowledge in the Biological Sciences | Chemical sciences | Expanding Knowledge in the Environmental Sciences |
Related Links
Publications
Syntheses and molecular structures of trans-bis(alkynyl) tetrakis-triethylphosphite ruthenium complexes
Publisher: Elsevier BV
Date: 10-2017
Dalton communications. Some unusual gold– and rhodium–rhenium clusters
Publisher: Royal Society of Chemistry (RSC)
Date: 1993
DOI: 10.1039/DT9930003145
Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations
Publisher: American Chemical Society (ACS)
Date: 11-11-2015
Abstract: A series of cross-conjugated compounds based on an (E)-4,4'-(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skeleton (1-6) have been synthesized. The linear optical absorption properties can be tuned by modification of the substituents at the 1 and 5 positions of the hexa-3-en-1,5-diynyl backbone (1: Si(CH(CH3)2)3, 2: C6H4C≡CSi(CH3)3, 3: C6H4COOCH3, 4: C6H4CF3, 5: C6H4C≡N, 6: C6H4C≡CC5H4N), although attempts to introduce electron-donating (C6H4CH3, C6H4OCH3, C6H4Si(CH3)3) substituents at these positions were h ered by the ensuing decreased stability of the compounds. Spectroelectrochemical investigations of selected ex les, supported by DFT-based computational studies, have shown that one- and two-electron oxidation of the 1,2-bis(triarylamine)ethene fragment also results in electronic changes to the perpendicular π-system in the hexa-3-en-1,5-diynyl branch of the molecule. These properties suggest that (E)-hexa-3-en-1,5-diynyl-based compounds could have applications in molecular sensing and molecular electronics.
Influence of surface coverage on the formation of 4,4′-bipyridinium (viologen) single molecular junctions
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7TC03624H
Abstract: Bipyridinium-containing wires give rise to molecular junctions with distinct geometries and conductance values.
New routes to organometallic molecular junctionsviaa simple thermal processing protocol
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9TC01305A
Abstract: Gold nanoparticle capped organometallic molecular junctions are prepared from a single source precursor by simple self-assembly and mild thermolysis.
Synthesis and redox properties of mono-, di- and tri-metallic platinum-ethynyl complexes based on the trans-Pt(C6H4N{C6H4OCH3-4}2)(C CR)(PPh3)2 motif
Publisher: Elsevier BV
Date: 2015
Structural characterization of ((9-fluorenylidene) (ferrocenyl)methyl)palladium iodide as the catalytic intermediate in the synthesis of 9-(ferrocenyl (ferrocenylethynyl)methylene)-9H-fluorene
Publisher: Informa UK Limited
Date: 18-07-2022
An Evolutionarily Conserved Enhancer Regulates Bmp4 Expression in Developing Incisor and Limb Bud
Publisher: Public Library of Science (PLoS)
Date: 12-06-2012
Mixing behaviour of a conjugated molecular wire candidate and an insulating fatty acid within Langmuir–Blodgett films
Publisher: Elsevier BV
Date: 08-2009
Spectroscopic properties and electronic structures of 17-electron half-sandwich ruthenium acetylide complexes, [Ru(CCAr)(L2)Cp′]+ (Ar=phenyl, p-tolyl, 1-naphthyl, 9-anthryl; L2=(PPh3)2, Cp′=Cp; L2=dpp
Publisher: Elsevier BV
Date: 07-2007
Syntheses of metal diynyl complexes: novel routes to all-carbon ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 1996
DOI: 10.1039/CC9960002405
Mixed-metal cluster chemistry. 11. Reactions of tungsten-iridium clusters with terminal alkynes and tungsten acetylides: X-ray crystal structures of Cp2W2Ir2(mu(4)-eta(2)-HC2Ph)(mu-CO)(4)(CO)(4) and CP2W2Ir3(mu(4)-eta(2)-C2C6H4Me-4)(mu-CO)(CO)(9)
Publisher: American Chemical Society (ACS)
Date: 20-11-1998
DOI: 10.1021/OM980692O
Oxidative Coupling of Ruthenium Alkenyl Acetylide Complexes as a Route to Dinuclear Complexes Featuring Carbon-Rich Bridging Ligands
Publisher: American Chemical Society (ACS)
Date: 02-11-2022
Ironvs.ruthenium: syntheses, structures and IR spectroelectrochemical characterisation of half-sandwich Group 8 acetylide complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0NJ03093G
Abstract: A synthetic ‘trick’ affording complexes [M(CCR)(dppe)Cp′] (M = Fe, Ru) in high purity directly from the reaction vessel is described.
Poly-carbon chemistry: reactions of the multi-site coordinated diyndiyl ligand in {Fe2(CO)6(μ-PPh2)}2(μ-η1,η2∶μ-η1,η2-CC–CC) with the nucleophiles P(OMe)3 and NHEt2
Publisher: Royal Society of Chemistry (RSC)
Date: 2001
DOI: 10.1039/B009797G
Controlling the Structural and Electrical Properties of Diacid Oligo(Phenylene Ethynylene) Langmuir–Blodgett Films
Publisher: Wiley
Date: 27-02-2013
Abstract: The preparation, characterization and electrical properties of Langmuir-Blodgett (LB) films composed of a symmetrically substituted oligomeric phenylene ethynylene derivative, namely, 4,4'-[1,4-phenylenebis(ethyne-2,1-diyl)]dibenzoic acid (OPE2A), are described. Analysis of the surface pressure versus area per molecule isotherms and Brewster angle microscopy reveal that good-quality Langmuir (L) films can be formed both on pure water and a basic subphase. Monolayer L films were transferred onto solid substrates with a transfer ratio of unity to obtain LB films. Both L and LB films prepared on or from a pure water subphase show a red shift in the UV/Vis spectrum of about 14 nm, in contrast to L and LB films prepared from a basic subphase, which show a hypsochromic shift of 15 nm. This result, together with X-ray photoelectron spectroscopic and quartz crystal microbalance experiments, conclusively demonstrate formation of one-layer LB films in which OPE2A molecules are chemisorbed onto gold substrates and consequently -COO-Au junctions are formed. In LB films prepared on a basic subphase the other terminal acid group is also deprotonated and associates with an Na(+) counterion. In contrast, LB films prepared from a pure water subphase preserve the protonated acid group, and lateral H-bonds with neighbouring molecules give rise to a supramolecular structure. STM-based conductance studies revealed that films prepared from a basic subphase are more conductive than the analogous films prepared from pure water, and the electrical conductance of the deprotonated films also coincides more closely with single-molecule conductance measurements. This result was interpreted not only in terms of better electron transmission in -COO-Au molecular junctions, but also in terms of the presence of lateral H-bonds in the films formed from pure water, which lead to reduced conductance of the molecular junctions.
Reaction of the Hexa-1,3,5-triyne Me3SiC CC≡CC CSiMe3with Ru4(CO)13( 3-PPh): Parallels with the Chemistry of Alkynes and Diynes
Publisher: Springer Science and Business Media LLC
Date: 09-2004
Spectroscopic and Computational Studies of the Ligand Redox Non-Innocence in Mono- and Binuclear Ruthenium Vinyl Complexes
Publisher: American Chemical Society (ACS)
Date: 10-03-2011
DOI: 10.1021/OM1010534
Ligand Redox Non-Innocence in Transition-Metal sigma-Alkynyl and Related Complexes
Publisher: Wiley
Date: 13-12-2012
Simultaneous Bridge-Localized and Mixed-Valence Character in Diruthenium Radical Cations Featuring Diethynylaromatic Bridging Ligands
Publisher: American Chemical Society (ACS)
Date: 24-10-2011
DOI: 10.1021/JA207827M
Abstract: A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}(2)(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV-vis-NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}(2)(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene 1,4-diethynyl-2,5-dimethoxybenzene 1,4-diethynylnaphthalene 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.
Synthesis, Structure and Physical Properties of “Wire-like” Metal Complexes
Publisher: American Chemical Society (ACS)
Date: 08-12-2020
Synthesis, Structure and Electrochemical Properties of Triarylamine Bridged Dicobaltdicarbon Tetrahedrane Clusters
Publisher: Springer Science and Business Media LLC
Date: 10-05-2012
Syntheses of complexes containing substituted 4-ethynylquinolines or 1-azabuta-1,3-dienes by addition of imines to a cationic butatrienylidene-ruthenium complex
Publisher: Elsevier BV
Date: 11-1999
New talent: Asia-Pacific
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9DT90116G
Abstract: Welcome to this themed issue of Dalton Transactions entitled “New Talent: Asia-Pacific.”
Coordinating Tectons: Bimetallic Complexes from Bipyridyl Terminated Group 8 Alkynyl Complexes
Publisher: American Chemical Society (ACS)
Date: 06-08-2014
DOI: 10.1021/OM500172R
Insulated molecular wires: inhibiting orthogonal contacts in metal complex based molecular junctions
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7NR01829K
Abstract: ‘Short circuits’ to ancillary ligands in metal complex molecular wires are identified and ‘insulated wires’ presented.
Iron Versus Ruthenium: Evidence for the Distinct Differences in the Electronic Structures of Hexa-1,3,5-triyn-1,6-diyl-bridged Complexes [Cp*(dppe)M}{μ-(C≡C)3}{M(dppe)Cp*}]+ (M =
Publisher: American Chemical Society (ACS)
Date: 21-01-2021
Experimental Validation of Quantum Circuit Rules in Molecular Junctions
Publisher: CSIRO Publishing
Date: 09-2021
DOI: 10.1071/CH21136
Abstract: A series of diarylacetylene (tolane) derivatives functionalised at the 4- and 4′-positions by thiolate, thioether, or amine groups capable of serving as anchor groups to secure the molecules within a molecular junction have been prepared and characterised. The series of compounds have a general form X-B-X, Y-B-Y, and X-B-Y where X and Y represent anchor groups and B the molecular bridge. The single-molecule conductance values determined by the scanning tunnelling microscope break-junction method are found to be in excellent agreement with the predictions made on the basis of a recently proposed ‘molecular circuit law’, which states ‘the conductance CH21136_IE1.gif of an asymmetric molecule X-B-Y is the geometric mean CH21136_IE2.gif of the conductance of the two symmetric molecules derived from it, CH21136_IE3.gif and CH21136_IE4.gif.’ The experimental verification of the circuit law, which holds for systems in which the constituent moieties X, B, and Y are weakly coupled and whose conductance takes place via off-resonance tunnelling, gives further confidence in the use of this relationship in the design of future compounds for use in molecular electronics research.
Electrochemical evidence for electronic interactions through the para-carborane skeleton in the novel tricluster [{Co2C2(SiMe3)(CO)4(dppm)}2(µ-CB10H10C)]
Publisher: Royal Society of Chemistry (RSC)
Date: 2001
DOI: 10.1039/B104307M
Abstract: The electrochemical properties of the title compound reveal electronic interactions between two dicobalt-dicarbon clusters via a 1,12-para-carborane cage.
Calcium phosphate stability on melt electrowritten PCL scaffolds
Publisher: Elsevier BV
Date: 03-2020
Oxidation Chemistry of Metal-Bonded C4 Chains: A Combined Chemical, Spectroelectrochemical, and Computational Study
Publisher: American Chemical Society (ACS)
Date: 17-02-2000
DOI: 10.1021/JA992002T
The synthesis, structure, reactivity and electrochemical properties of ruthenium complexes featuring cyanoacetylide ligands
Publisher: Elsevier BV
Date: 02-2006
Cycloaddition of aromatic imines to a ruthenium butatrienylidene complex: synthesis of 4-ethynylquinoline and 1-azabuta-1,3-diene complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 1997
DOI: 10.1039/A700663B
Advances in single-molecule junctions as tools for chemical and biochemical analysis
Publisher: Springer Science and Business Media LLC
Date: 27-04-2023
Molecular Wires using (Oligo)pyrroles as Connecting Units: An Electron Transfer Study
Publisher: American Chemical Society (ACS)
Date: 05-09-2013
DOI: 10.1021/OM4007533
The synthesis, structure, and electrochemical properties of Fe(C≡CC≡N)(dppe)Cp and related compounds
Publisher: Canadian Science Publishing
Date: 02-2006
DOI: 10.1139/V05-238
Abstract: The cyanoacetylide complex Fe(C≡CC≡N)(dppe)Cp (3) is readily obtained from sequential reaction of Fe(C≡CSiMe 3 )(dppe)Cp with methyllithium and phenyl cyanate. Complex 3 is a good metalloligand, and coordination to the metal fragments [RhCl(CO) 2 ], [Ru(PPh 3 ) 2 Cp] + , and [Ru(dppe)Cp*] + affords the corresponding cyanoaceylide-bridged heterobimetallic complexes. In the case of the 36-electron complexes [Cp(dppe)Fe-C≡CC≡N-ML n ] n + , spectroscopic and structural data are consistent with a degree of charge transfer from the iron centre to the rhodium or ruthenium centre via the C 3 N bridge, giving rise to a polarized ground state. Electrochemical and spectroelectrochemical methods reveal significant interactions between the metal centres in the oxidized (35 electron) derivatives, [Cp(dppe)Fe-C≡CC≡N-ML n ] (n+1)+ . Key words: cyanide, cyanoacetylide, crystal structure.
Exploring relationships between chemical structure and molecular conductance: from α,ω-functionalised oligoynes to molecular circuits
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3NR01034A
Abstract: Rules governing the conductance of molecular circuits assembled from components assembled in series are assessed.
Syntheses, Structures, Some Reactions, and Electrochemical Oxidation of Ferrocenylethynyl Complexes of Iron, Ruthenium, and Osmium
Publisher: American Chemical Society (ACS)
Date: 23-09-2005
DOI: 10.1021/OM050483L
Electronic interactions in bridged bis(cluster) assemblies – a comparison of para-CB10H10C, para-C6H4 and C4 bridges
Publisher: Elsevier BV
Date: 11-2005
21 Organometallic chemistry of bi- and poly-nuclear complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B311798G
Building large-scale unimolecular scaffolding for electronic devices
Publisher: Elsevier BV
Date: 12-2022
Mixed-metal cluster chemistry. 28. Core enlargement of tungsten-iridium clusters with alkynyl, ethyndiyl, and butadiyndiyl reagents
Publisher: American Chemical Society (ACS)
Date: 02-04-2005
DOI: 10.1021/IC050040+
Abstract: Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c) R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.
Rapid Markovnikov addition of HCl to a pendant alkyne: evidence for a quinoidal cumulene
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4CC09696G
Abstract: The reaction of the vinylidene cations trans -[Ru(CCH–C 6 H 2 -2,5-R 2 -4-CCH)Cl(dppm) 2 ] + (R = H, Me) with chloride results in Markovnikov addition of HCl to the terminal alkyne, suggesting the intermediacy of a quinoidal cumulene complex.
Influence of P‐Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl‐Substituted Phospholes
Publisher: Wiley
Date: 30-06-2015
Abstract: 2,5‐Diferrocenyl‐1‐Ar‐1 H ‐phospholes 3 a – e (Ar=phenyl ( a ), ferrocenyl ( b ), mesityl ( c ), 2,4,6‐triphenylphenyl ( d ), and 2,4,6‐tri‐ tert ‐butylphenyl ( e )) have been prepared by reactions of ArPH 2 ( 1 a – e ) with 1,4‐diferrocenyl butadiyne. Compounds 3 b – e have been structurally characterized by single‐crystal XRD analysis. Application of the sterically demanding 2,4,6‐tri‐ tert ‐butylphenyl group led to an increased flattening of the pyramidal phosphorus environment. The ferrocenyl units could be oxidized separately, with redox separations of 265 ( 3 b ), 295 ( 3 c ), 340 ( 3 d ), and 315 mV ( 3 e ) in [N n Bu 4 ][B(C 6 F 5 ) 4 ] these values indicate substantial thermodynamic stability of the mixed‐valence radical cations. Monocationic [ 3 b ] + –[ 3 e ] + show intervalence charge‐transfer absorptions between 4650 and 5050 cm −1 of moderate intensity and half‐height bandwidth. Compounds 3 c – e with bulky, electron‐rich substituents reveal a significant increase in electronic interactions compared with less demanding groups in 3 a and 3 b .
The Coordination and Derivative Chemistry of Phosphinoalkynes on Polymetallic Frameworks and Related Systems
Publisher: Springer Science and Business Media LLC
Date: 25-01-2008
Syntheses, Structures, and Spectro-electrochemistry of {Cp*(PP)Ru}C⋮CC⋮C{Ru(PP)Cp*} (PP = dppm, dppe) and Their Mono- and Dications
Publisher: American Chemical Society (ACS)
Date: 27-06-2003
DOI: 10.1021/OM030015G
Facile Decarboxylation of Propiolic Acid on a Ruthenium Center and Related Chemistry
Publisher: American Chemical Society (ACS)
Date: 08-2012
DOI: 10.1021/OM300157W
Some Ruthenium Derivatives of Penta-1,4-diyn-3-one
Publisher: American Chemical Society (ACS)
Date: 16-05-2013
DOI: 10.1021/OM400208Q
Long range charge transfer in trimetallic mixed-valence iron complexes mediated by redox non-innocent cyanoacetylide ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4DT00614C
Abstract: A redox active 9-atom, 10-bond –CC–CN{Fe(dppx) 2 }NC–CC– bridge is shown to be effective at promoting electron transfer between metal centres separated by some 15 Å.
Improved syntheses of bis(ethynyl)-para-carboranes, 1,12-(RCC)2-1,12-C2B10H10 and 1,10-(RCC)2-1,10-C2B8H8 (R=H or Me3Si)
Publisher: Elsevier BV
Date: 09-2006
Syntheses and Structures of Buta-1,3-Diynyl Complexes from “on Complex” Cross-Coupling Reactions
Publisher: American Chemical Society (ACS)
Date: 17-02-2015
DOI: 10.1021/OM501186C
A Re-evaluation of the Photophysical Properties of 1,4-Bis(phenylethynyl)benzene: A Model for Poly(phenyleneethynylene)
Publisher: American Chemical Society (ACS)
Date: 13-06-2002
DOI: 10.1021/JA025568H
Abstract: Photophysical measurements, recorded in aerated cyclohexane at 283 K, indicate that 1,4-bis(phenylethynyl)benzene behaves in a conventional manner, undergoing emission from the lowest vibrational level of the first excited singlet state there is no evidence for aggregation of this material in cyclohexane solution in the concentration range (1-250) x 10(-6) mol dm(-3). However, in highly viscous, low-temperature glasses, the material does exhibit inhomogeneous fluorescence behavior, and wavelength-dependent excitation and emission spectra, indicative of a slow rate of relaxation of conformers of the excited states compared to the rate of fluorescence.
Syntheses, Spectroelectrochemical Studies, and Molecular and Electronic Structures of Ferrocenyl Ene-diynes
Publisher: American Chemical Society (ACS)
Date: 09-08-2013
DOI: 10.1021/OM400535Y
Structural and electronic variations in cobalt–alkyne clusters †
Publisher: Royal Society of Chemistry (RSC)
Date: 2001
DOI: 10.1039/B008445J
An efficient synthesis of polyynyl and polyynediyl complexes of ruthenium(II) †
Publisher: Royal Society of Chemistry (RSC)
Date: 1999
DOI: 10.1039/A905174K
Langmuir–Blodgett films incorporating molecular wire candidates of ester-substituted oligo(phenylene–ethynylene) derivatives
Publisher: Elsevier BV
Date: 12-2008
Molecular Wires: An Overview of the Building Blocks of Molecular Electronics
Publisher: Springer Singapore
Date: 2016
Looking Ahead: Challenges and Opportunities in Organometallic Chemistry
Publisher: American Chemical Society (ACS)
Date: 04-01-2011
DOI: 10.1021/OM100919R
Quanteninterferenz in gemischtvalenten Komplexen: Modifikation elektronischer Kopplung durch Substituenteneffekte
Publisher: Wiley
Date: 10-10-2022
Abstract: In 2‐ und 5‐Position einer Phenylenbrücke eines schwach koppelnden gemischtvalenten [{Cp*(dppe)RuC≡C} 2 (μ‐1,3‐C 6 H 4 )] + Komplexes hat ein OMe‐Substituent nur geringen Einfluss auf dessen Elektronenstruktur. In 4‐Position hingegen erhöht dieser die elektronische Delokalisation im Grundzustand sowie die Intensität des IVCT‐Überganges. Schwingungsfrequenzen und TDDFT‐Berechnungen (LH20t‐D3(BJ), def2‐SVP, COSMO (CH 2 Cl 2 )) an ([{Cp*(dppe)RuC≡C} 2 (μ‐1,3‐C 6 H 3 ‐ n ‐OMe)] + ( n = 2, 4, 5) Modellen zeigen eine exzellente Übereinstimmung mit experimentellen Ergebnissen. Die stärkere Kopplung im Grundzustand geht auf eine veränderte Zusammensetzung des β‐HOSO zurück, verursacht durch den 4‐OMe Substituenten und dessen ortho ‐ oder para ‐Stellung zu jedem der Metallfragmente. Die Intensität des IVCT‐Überganges erhöht sich mit stärkerer β‐HOSO‐ und β‐LUSO‐Überlappung. Die relativen Phasen von β‐HOSO und β‐LUSO im 4‐OMe‐substituierten Komplex sind in Einklang mit den Vorhersagen über konstruktive Quanteninterferenz, basierend auf molekularen Schaltkreisregeln.
Homoleptic transition metal acetylides
Publisher: Elsevier BV
Date: 2011
Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes
Publisher: Elsevier BV
Date: 12-2012
A simple synthesis of trans-RuCl(CCR)(dppe)2 complexes and representative molecular structures
Publisher: Elsevier BV
Date: 07-2009
Synthesis, photoluminescence, catalysis and multilayer film assembly of an ethynylpyridine platinum compound
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CE00382D
Some chemistry of Re2( μ-H) ( μ-C2Ph) (CO)8: X-ray structures of Re2( μ-H) ( μ-C2Ph) (CO)6(PMe3)2, Re2{μ-Au(PPh3)}( μ-C2Ph) (CO)8,Re2 ( μ-X) (μ-dppm) ( μ-C2Ph) (CO)6 [X = H, Br and Au(PPh3)] and Re2(
Publisher: Elsevier BV
Date: 05-1996
Preparation and molecular structures of the decanuclear diynyl-ruthenium-silver and -copper complexes [M6{μ3-CCCC[Ru(dppe)Cp∗]}4(μ-dppm)2](BF4)2 (M=Ag, Cu)
Publisher: Elsevier BV
Date: 05-2010
Synthesis and (Spectro)electrochemical Behavior of 2,5-Diferrocenyl-1-phenyl-1H-phosphole
Publisher: American Chemical Society (ACS)
Date: 08-05-2013
DOI: 10.1021/OM400201B
Facile photoinduced charge separation through a cyanoacetylide bridge in a heterobimetallic Fe(ii)–Re(i) complex
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B811357B
Abstract: Photoinduced Fe-to-bpy charge transfer in [{Cp(dppe)Fe}(mu-C[triple bond]CC[triple bond]N){Re(CO)(3)(bpy)}]PF(6) has been observed by ps-TRIR spectroscopy, supported by UV-Vis/IR spectroelectrochemistry and DFT calculations.
Alkyne substituted mononuclear photocatalysts based on [RuCl(bpy)(tpy)]+
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT01278C
Abstract: The introduction of ‘wire-like’ arylene ethynylene substituent to the prototypical water oxidation catalyst precursor [RuCl(2,2′-bipyridine)(2,2′:6′,2′′-terpyridine)]PF 6 does not significantly alter the photostability of the compounds, nor the ability of the complexes to oxidise 4-methoxybenzyl alcohol to 4-methoxybenzaldehyde.
Crystal, Molecular and Electronic Structure of N,N′‐Diphenyl‐N,N′‐bis(2,4‐dimethylphenyl)‐(1,1′‐biphenyl)‐4,4′‐diamine and the Corresponding Radical Cation
Publisher: Wiley
Date: 19-12-2003
Abstract: Oxidation of N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD, 1 a) and N,N'-diphenyl-N,N'-bis(2,4-dimethylphenyl)-(1,1'-biphenyl)-4,4'-diamine (1 b) with SbCl(5) affords the corresponding radical cations quantitatively. The crystal and molecular structure of 1 b and [1 b]SbCl(6), the first tetraphenyl benzidene derivatives to be characterised crystallographically in both the neutral and radical cation states, reveal molecular parameters in agreement with the predictions made on the basis of DFT studies. Analysis of the NIR transition in the radical cations [1](+) (.) allows an estimate of the electronic coupling parameter V (1 a(+) (.) 3200 cm(-1) 1 b(+) (.) 3300 cm(-1)), the reorganisation energy lambda(1 a(+) (.) 7500 cm(-1) 1 b(+) (.) 7800 cm(-1)), and the linear coupling constant l (1 a(+) (.) 3100 cm(-1) 1 b(+) (.) 2700 cm(-1)) of the symmetric mode.
Further Chemistry of Ruthenium Alkenyl Acetylide Complexes: Routes to Allenylidene Complexes via a Series of Electrophilic Addition Reactions
Publisher: American Chemical Society (ACS)
Date: 27-07-2020
Studies of the S1 state in a prototypical molecular wire using picosecond time-resolved spectroscopiesElectronic supplementary information (ESI) available: time-resolved emission spectra, and transien
Publisher: Royal Society of Chemistry (RSC)
Date: 2003
DOI: 10.1039/B307005K
Abstract: Picosecond time-resolved resonance Raman spectroscopy, TR3, reveals an intense acetylenic band in the S1 state of the prototypical molecular wire 1,4-bis(phenylethynyl)benzene.
Cover Feature: Further Evidence for ‘Extended’ Cumulene Complexes: Derivatives from Reactions with Halide Anions and Water (Chem. Eur. J. 32/2020)
Publisher: Wiley
Date: 08-05-2020
Structural, spectroscopic, electrochemical and computational studies of C,C′-diaryl-ortho-carboranes, 1-(4-XC6H4)-2-Ph-1,2-C2B10H10 (X = H, F, OMe, NMe2, NH2, OH and O−)
Publisher: Springer Science and Business Media LLC
Date: 11-11-2008
Sandwich and half-sandwich metal complexes derived from cross-conjugated 3-methylene-penta-1,4-diynes
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6DT04470K
Abstract: Mono-, di- and trimetallic derivatives of the cross-conjugated 3-methylene-penta-1,4-diyne moiety have been prepared, and studied by (spectro)electrochemical methods.
Polycarbon Ligand Complexes: Synthesis, Molecular Structures, and Selected EHMO Studies of Ru4, Ru5, and Ru6 Clusters with Carbon Ligands Derived from Phosphinodiynes
Publisher: American Chemical Society (ACS)
Date: 13-05-1998
DOI: 10.1021/OM9800593
Molecular electronics: an Australian perspective
Publisher: CSIRO Publishing
Date: 12-07-2023
DOI: 10.1071/CH23008
Single Gold Atom Containing Oligo(phenylene)ethynylene: Assembly into LB Films and Electrical Characterization
Publisher: American Chemical Society (ACS)
Date: 17-12-2014
DOI: 10.1021/JP510078W
Refining the Interpretation of Near‐Infrared Band Shapes in a Polyynediyl Molecular Wire
Publisher: Wiley
Date: 12-06-2013
Abstract: Spinning to improve (band) shape: A blend of theoretical and experimental work demonstrates that the rotational conformation of mixed-valence complexes influences the low-energy (NIR) transitions in such molecules. Interpretations of the NIR band shapes are presented.
Preparation and Characterization of Langmuir and Langmuir−Blodgett Films from a Nitrile-Terminated Tolan
Publisher: American Chemical Society (ACS)
Date: 23-01-2007
DOI: 10.1021/CM062524P
Back matter
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B923644A
Rip It off: Nitro to Nitroso Reduction by Iron Half-Sandwich Complexes
Publisher: American Chemical Society (ACS)
Date: 12-03-2021
Iron versus Ruthenium: Clarifying the Electronic Differences between Prototypical Mixed-Valence Organometallic Butadiyndiyl Bridged Molecular Wires
Publisher: American Chemical Society (ACS)
Date: 30-04-2018
Some Chemistry of Diynyl - Tungsten Complexes
Publisher: CSIRO Publishing
Date: 2001
DOI: 10.1071/CH01103
Organometallic Complexes for Nonlinear Optics. 45. Dispersion of the Third-Order Nonlinear Optical Properties of Triphenylamine-Cored Alkynylruthenium Dendrimers
Publisher: Wiley
Date: 12-06-2009
Mix and (Mis)match: further studies of the electronic structure and mixed-valence characteristics of 1,4-diethynylbenzene-bridged bimetallic complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0DT01794A
Abstract: Infra-red spectroelectrochemical studies of [{Cp′(CO) x M′}(μ-CCC 6 H 4 CC){M(PP)Cp′}] n+ [ n = 0, 1] illustrate limited ground-state interactions in these donor–acceptor compounds and the localised nature of the one-electron redox processes.
Electrical characterization of single molecule and Langmuir–Blodgett monomolecular films of a pyridine-terminated oligo(phenylene-ethynylene) derivative
Publisher: Beilstein Institut
Date: 11-05-2015
DOI: 10.3762/BJNANO.6.116
Abstract: Monolayer Langmuir–Blodgett (LB) films of 1,4-bis(pyridin-4-ylethynyl)benzene ( 1 ) together with the “STM touch-to-contact” method have been used to study the nature of metal–monolayer–metal junctions in which the pyridyl group provides the contact at both molecule–surface interfaces. Surface pressure vs area per molecule isotherms and Brewster angle microscopy images indicate that 1 forms true monolayers at the air–water interface. LB films of 1 were fabricated by deposition of the Langmuir films onto solid supports resulting in monolayers with surface coverage of 0.98 × 10 −9 mol·cm −2 . The morphology of the LB films that incorporate compound 1 was studied using atomic force microscopy (AFM). AFM images indicate the formation of homogeneous, monomolecular films at a surface pressure of transference of 16 mN·m −1 . The UV–vis spectra of the Langmuir and LB films reveal that 1 forms two dimensional J-aggregates. Scanning tunneling microscopy (STM), in particular the “STM touch-to-contact” method, was used to determine the electrical properties of LB films of 1 . From these STM studies symmetrical I–V curves were obtained. A junction conductance of 5.17 × 10 −5 G 0 results from the analysis of the pseudolinear (ohmic) region of the I–V curves. This value is higher than that of the conductance values of LB films of phenylene-ethynylene derivatives contacted by amines, thiols, carboxylate, trimethylsilylethynyl or acetylide groups. In addition, the single molecule I – V curve of 1 determined using the I ( s ) method is in good agreement with the I–V curve obtained for the LB film, and both curves fit well with the Simmons model. Together, these results not only indicate that the mechanism of transport through these metal–molecule–metal junctions is non-resonant tunneling, but that lateral interactions between molecules within the LB film do not strongly influence the molecule conductance. The results presented here complement earlier studies of single molecule conductance of 1 using STM-BJ methods, and support the growing evidence that the pyridyl group is an efficient and effective anchoring group in sandwiched metal–monolayer–metal junctions prepared under a number of different conditions.
Metal Complexes for Molecular Electronics
Publisher: Elsevier
Date: 2021
Spectroscopic Properties and Electronic Structure of the Cycloheptatrienyl Molybdenum Alkynyl Complexes [Mo(C≡CR)(Ph2PCH2CH2PPh2)(η-C7H7
Publisher:
American Chemical Society (ACS)
Date:
08-03-2010
DOI:
10.1021/OM901074B
Acetylene Used as a New Linker for Molecular Junctions in Phenylene–Ethynylene Oligomer Langmuir–Blodgett Films
Publisher: American Chemical Society (ACS)
Date: 11-04-2012
DOI: 10.1021/JP301854N
Synthesis, structure and redox chemistry of the aminoallenylidene complex [Mo{C C C(Me)NEt2}(dppe)(η-C7H7)][BPh4]
Publisher: Elsevier BV
Date: 2017
Low variability of single-molecule conductance assisted by bulky metal–molecule contacts
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6RA15477H
Abstract: A detailed study of the trimethylsilylethynyl moiety, –CCSiMe 3 (TMSE), as an anchoring group, using a combination of experiment and DFT is presented.
Reactions of M(CCCCR)(CO)3Cp [M=Mo, W; R=H, Fe(CO)2Cp, M(CO)3Cp] with cobalt carbonyls: X-ray structures of {Cp(OC)8Co2M(μ3-C)}CC{(μ3-C)Co2M′(CO)8Cp} (M=M′=Mo, W; M=Mo, M′=W)
Publisher: Elsevier BV
Date: 04-1999
In-situ generation and analysis of charge transfer materials using an OTTLE cell and resonance Raman scatteringElectronic supplementary information (ESI) available: BPW91/6-31G(d) predicted vibrationa
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B402015D
Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems
Publisher: Elsevier BV
Date: 10-2004
Polymetallation of alkenes: Formation of some complexes containing branched chain carbon-rich ligands
Publisher: Elsevier BV
Date: 10-2006
Practice chains of production and consumption: mediatized practices across social fields
Publisher: Informa UK Limited
Date: 02-2010
Molecular Structure–(Thermo)electric Property Relationships in Single-Molecule Junctions and Comparisons with Single- and Multiple-Parameter Models
Publisher: American Chemical Society (ACS)
Date: 19-02-2021
DOI: 10.1021/JACS.0C11605
Cyclopentadienyl-Ruthenium and -Osmium Chemistry. XL. X-Ray Crystal Structures of MBr (PPh3)2(η-C5H5).CH2Cl2 (M = Ru, Os)
Publisher: CSIRO Publishing
Date: 1995
DOI: 10.1071/CH9951887
Abstract: The crystal and molecular structures of MBr (PPh3)2(η-C5H5).CH2Cl2 (M = Ru and Os) have been determined. A revised synthesis of the bromo osmium complex is given. The coordination geometry about the metal atom is based on a distorted octahedron with one face being occupied by the cyclopentadienyl group [average Ru -C(Cp) 2.214(3), Os-C(Cp) 2.177(3)Ǻ] and the other by the bromide [ Ru -Br 2.5683(8), Os-Br 2.5438(9)Ǻ] and the two phosphorus atoms [ Ru -P 2.323(2), 2.329(1) Os-P 2.290(2), 2.297(2)Ǻ]. Structural parameters are compared with those of the corresponding chloro complexes and differ only minimally. Crystals of MBr (PPh3)2(η-C5H5).CH2Cl2 are triclinic, space group Pī , with unit cell dimensions ( Ru [Os]): a 14.374(5) [14.276(4)], b 14.057(4) [13.959(3)], c 10.012(5) [9.903(3)]Ǻ, α 99.43(3) [99.79(2)], β 105.60(3) [105.74(2)], γ 100.42(3) [100.39(2)]°, V 1868(1) [1817.7(9)] Ǻ3, Z 2. The structures were refined by a full-matrix least-squares procedure to R 0.050 [0.036] for 7365 [5108] reflections with I ≥ 3σ(I).
Turning the Tap: Conformational Control of Quantum Interference to Modulate Single‐Molecule Conductance
Publisher: Wiley
Date: 31-10-2019
Abstract: Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum‐interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular‐design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta ‐substituted phenylene ethylene‐type oligomers ( m ‐OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular‐scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic‐ratio and orbital‐product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single‐molecule devices with desirable electronic functions.
Multifunctional switching properties of “wire-like” dinuclear ruthenium bis-alkynyl spiropyran complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2DT03045D
Abstract: Whilst inert to electrochemical stimulus, acid-induced ring-opening of an ethynyl spiropyran ligand in Ru complexes proceeds to form the protonated merocyanine, that can be switched from the Z - to E -form by UV light.
Syntheses and molecular structures of group 8 benzonitrile complexes
Publisher: Elsevier BV
Date: 11-2005
Towards an understanding of structure–property relationships in hole-transport materials: The influence of molecular conformation on oxidation potential in poly(aryl)amines
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B417962E
Synthesis of a diferrocenylvinylidene complex by migration of a ferrocenyl substituent
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1CC00605C
Abstract: The synthesis of the first diferrocenyl vinylidene complex is reported via migration of a ferrocenyl group along an unsaturated CC bond. Bis(alkynes) with phenyl and ferrocenyl groups in various positions gave bimetallic bis(vinylidene) complexes.
Excited State Mixed‐Valence Complexes: From the Special Pair to the Creutz–Taube Ion and Beyond
Publisher: Wiley
Date: 08-02-2023
Abstract: Compounds and complexes with mixed‐valence electronic ground states, such as the Creutz–Taube ion, have proven to be excellent vehicles through which to study intramolecular electron‐transfer processes. In a recent contribution by Cadranel and co‐workers, time‐resolved pump‐probe spectroscopy reveals photo‐induced metal‐to‐bridge charge transfer within the homovalent analogue of the Creutz–Taube ion, [{(NH 3 ) 5 Ru}(μ‐pz){Ru(NH 3 ) 5 }] 4+ , giving rise to two closely lying excited states with mixed‐valence character, one with a shorter lifetime ( τ =136 ps) and weakly‐coupled (Robin‐Day Class II) character, the other a longer‐lived ( τ =2.8 ns) configurational isomer with more delocalized electronic structure. Electron transfer reactions from the longer‐lived species demonstrate analogies with the photo‐induced reactions of the photosynthetic special pair, suggesting this state as a reference system for excited state mixed‐valency, and a framework from which to explore photocatalytic reactions.
Modulation of Charge Distribution in Cobalt-α-Diimine Complexes toward Valence Tautomerism.
Publisher: American Chemical Society (ACS)
Date: 27-10-2022
DOI: 10.1021/ACS.INORGCHEM.2C02659
Abstract: Valence tautomerism (VT) and spin crossover (SCO) are promising avenues for developing a range of molecular materials for sensing, memory, and optoelectronic applications. However, these phenomena arise only when specific metal-ligand combinations are employed. The underexplored combination of cobalt(II/III) paired with bis((aryl)imino)acenapthene (Ar-BIAN) ligands, which can exist as neutral Ar-BIAN
Synthesis and Characterization of Dithia[3.3]paracyclophane-Bridged Binuclear Ruthenium Vinyl and Alkynyl Complexes
Publisher: American Chemical Society (ACS)
Date: 19-07-2012
DOI: 10.1021/OM300338J
Simplifying the conductance profiles of molecular junctions: the use of the trimethylsilylethynyl moiety as a molecule–gold contact
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2DT31825C
Abstract: Conductance across a metal|molecule|metal junction is strongly influenced by the molecule-substrate contacts, and for a given molecular structure, multiple conductance values are frequently observed and ascribed to distinct binding modes of the contact at each of the molecular termini. Conjugated molecules containing a trimethylsilylethynyl terminus, -C≡CSiMe(3) give exclusively a single conductance value in I(s) measurements on gold substrates, the value of which is similar to that observed for the same molecular backbone with thiol and amine based contacting groups when bound to under-coordinated surface sites.
A simple “palladium-free” synthesis of phenyleneethynylene-based molecular materials revisited
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B502950C
Broad-Band NIR Transient Absorption Spectroscopy of an All-Carbon-Bridged Bimetallic Radical Cation Complex
Publisher: American Chemical Society (ACS)
Date: 05-08-2015
From an Organometallic Monolayer to an Organic Monolayer Covered by Metal Nanoislands: A Simple Thermal Protocol for the Fabrication of the Top Contact Electrode in Molecular Electronic Devices
Publisher: Wiley
Date: 26-06-2014
Directionally Oriented LB Films of an OPE Derivative: Assembly, Characterization, and Electrical Properties
Publisher: American Chemical Society (ACS)
Date: 03-03-2011
DOI: 10.1021/LA104734J
Abstract: Langmuir films have been fabricated from 4-[4'-(4''-thioacetyl-phenyleneethynylene)-phenyleneethynylene]-aniline (NOPES) after cleavage of the thioacetyl protecting group. Characterization by surface pressure vs area per molecule isotherms and Brewster angle microscopy reveal the formation of a high quality monolayer at the air-water interface. One layer Langmuir-Blodgett (LB) films were readily fabricated by the transfer of the NOPES Langmuir film onto solid substrates. X-ray photoelectron spectroscopy (XPS), surface polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), and quartz crystal microbalance (QCM) experiments conclusively demonstrate the formation of one layer LB films in which the functional group associated with binding to the substrate can be tailored by the film transfer conditions. Using LB methods this molecule could be transferred to gold s les with either the amine or thiol group attached to the gold surface. The amine group is directly attached to the gold substrate (Au-NH(2)-OPE-SH) when the substrate is initially immersed in the subphase and withdrawn during the transfer process in contrast, monomolecular films in which the thiolate group is attached to the gold substrate (Au-S-OPE-NH(2)) are obtained when the substrate is initially out of the subphase and immersed during the transfer process. The morphology of these films was analyzed by atomic force microscopy (AFM), showing the formation of homogeneous layers. Film homogeneity was confirmed by cyclic voltammetry, which revealed a large passivation of gold electrodes covered by NOPES monolayers. Electrical properties for both polar orientated junctions have been investigated by scanning tunnelling microscopy (STM), with both orientations featuring a nonrectifying behavior.
Electronic Structure of Ruthenium(II) Polyynyl Complexes
Publisher: American Chemical Society (ACS)
Date: 25-09-2001
DOI: 10.1021/OM010304+
Molecular Electronics: History and Fundamentals
Publisher: CSIRO Publishing
Date: 2016
DOI: 10.1071/CH15634
Abstract: The increasing difficulties of meeting ‘Moore’s Law’ rates of progress in conventional semiconductor electronics, coupled with the advent of methods capable of measuring the electronic properties of single molecules in a laboratory setting, have seen a surge of activity in the field of molecular electronics over the last decade. However, the concepts of molecular electronics are far from new, and the basic premise and ideas of molecular electronics have been shadowing those of solid-state semiconductor electronics since the middle of the 20th century. In this Primer Review, we introduce the topic of molecular electronics, drawing on some of the earliest expressions of the fundamental concepts, and summarizing key concepts to provide the interested reader with an entry to this fascinating field of science and emerging technology.
Coordinating Tectons. Experimental and Computational Infrared Data as Tools To Identify Conformational Isomers and Explore Electronic Structures of 4-Ethynyl-2,2′-bipyridine Complexes
Publisher: American Chemical Society (ACS)
Date: 04-05-2017
From ferrocene to fluorine-containing penta-substituted derivatives and all points in-between; or, how to increase the available chemical space
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9OB01885A
Abstract: The syntheses of di-, tri-, tetra- and pentasubstituted derivatives of fluoroferrocene from ferrocene are reported. These strategies enhance the available chemical space for future applications in medicinal and organic materials chemistry.
Ruthenium Complexes of C,C‘-Bis(ethynyl)carboranes: An Investigation of Electronic Interactions Mediated by Spherical Pseudo-aromatic Spacers
Publisher: American Chemical Society (ACS)
Date: 23-02-2008
DOI: 10.1021/JA0779755
Abstract: The complexes [Ru(1-C[triple bond]C-1,10-C2B8H9)(dppe)Cp*] (3a), [Ru(1-C[triple bond]C-1,12-C2B10H11)(dppe)Cp*] (3b), [{Ru(dppe)Cp*}2{mu-1,10-(C[triple bond]C)2-1,10-C2B8H8}] (4a) and [{Ru(dppe)Cp*}2{mu-1,12-(C[triple bond]C)2-1,12-C2B10H10}] (4b), which form a representative series of mono- and bimetallic acetylide complexes featuring 10- and 12-vertex carboranes embedded within the diethynyl bridging ligand, have been prepared and structurally characterized. In addition, these compounds have been examined spectroscopically (UV-vis-NIR, IR) in all accessible redox states. The significant separation of the two, one-electron anodic waves observed in the cyclic voltammograms of the bimetallic complexes 4a and 4b is largely independent of the nature of the electrolyte and is attributed to stabilization of the intermediate redox products [4a]+ and [4b]+ through interactions between the metal centers across a distance of ca. 12.5 A. The mono-oxidized bimetallic complexes [4a]+ and [4b]+ exhibit spectroscopic properties consistent with a description of these species in terms of valence-localized (class II) mixed-valence compounds, including a unique low-energy electronic absorption band, attributed to an IVCT-type transition that tails into the IR region. DFT calculations with model systems [4a-H]+ and [4b-H]+ featuring simplified ligand sets reproduce the observed spectroscopic data and localized electronic structures for the mixed-valence cations [4a]+ and [4b]+.
Coordinatively and Electronically Unsaturated Tetraruthenium Clusters: Reversible Triple CO Addition to Ru4(CO)9(μ-PPh2)[μ4-Ph2PCC(Ph)CC(Ph)]
Publisher: American Chemical Society (ACS)
Date: 18-06-1998
DOI: 10.1021/OM980168H
Metal bis(acetylide) complex molecular wires: concepts and design strategies
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8DT02103A
Abstract: This Perspective highlights relationships between chemical features of metal bis(acetylide) complexes and their electrical response in a molecular junction.
From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1DT03430H
Abstract: Impact of successive fluorinations onto redox, spectroscopic and NMR properties of ferrocene.
Experimental and computed dipole moments in donor–bridge–acceptor systems with p-phenylene and p-carboranediyl bridges
Publisher: Institute of Organic Chemistry & Biochemistry
Date: 2009
DOI: 10.1135/CCCC2008154
Abstract: Dipole moments were measured for a series of substituted benzenes, biphenyls, terphenyls, C -monoaryl- and C , C ′-diaryl- p -carboranes. For the donor–bridge–acceptor systems, Me 2 N–X–NO 2 , where X is 1,4-phenylene, biphenyl-4,4′-diyl, terphenyl and 1,4-C 6 H 4 - p -CB 10 H 10 C-1,4-C 6 H 4 , the measured interaction dipole moments are 1.36, 0.74, 0.51 and 0.00 D, respectively. The magnitude of the dipole moment reflects the ability of the bridge to transmit electronic effects between donor and acceptor groups. Thus, whilst the 1,4-phenylene bridges allow moderate electronic interactions between the remote groups, the p -carboranediyl unit is less efficient as a conduit for electronic effects. Averaged dipole moments computed at the DFT (B3LYP/6-31G*) level of theory from two distinct molecular conformers are in good agreement with the experimental values. Examination of the calculated electronic structures provides insight into the nature of the interactions between the donor and acceptor moieties through these 2D and 3D aromatic bridges. The most significant cooperative effect of the bridge on the dipole moment occurs in systems where there is some overlap between the HOMO and LUMO orbitals. This orbital overlap criterion may help to define the difference between “push-pull” systems in which electronic effects are mediated by the bridging moiety, and simpler systems in which the bridge acts as an electronically innocent spacer unit and through-space charge transfer/separation is dominant.
Synthesis and Structure of the Cluster Ion Pair {Ru3(CO)9[μ-P(NPri2)2]3}{Ru6(CO)15(μ6-C)[μ-P(NPr
Publisher: American Chemical Society (ACS)
Date: 18-02-2000
DOI: 10.1021/IC990195F
Abstract: The compound [Ru3(CO)9[mu-P(NPri2)2]3][Ru6(CO)15(mu 6-C)[mu-P(NPri2)2]] (1), obtained via the addition of PCl(NPri2)2 to K2[Ru4(CO)13], crystallizes in the monoclinic space group P2l/c with a = 15.537(8) A, b = 36.151(16) A, c = 19.407(5) A, beta = 91.14(2) degrees, Z = 4, and R = 0.069 for 8006 observed reflections. The unit cell is unusual in that it contains both a typical octahedral Ru6 cluster anion (1a), featuring an encapsulated carbide, and a symmetrical phosphido bridge, in addition to a 50-electron trinuclear cluster cation [Ru3(CO)9[mu-P(NPri2)2]3]+ (1c). The latter, with approximate D3h symmetry, exhibits long Ru-Ru distances (> or = 3.15 A). Among the family of clusters with M3(mu-PR2)3 cores and different numbers of both electrons (TEC) and terminal ligands (LxLyLz), 1c is unique in that it is a 333 stereotype with 50 valence electrons. MO calculations permit us to predict the existence of redox congeners of 1c clusters and related 48e Re3 clusters. This work also presents a summary of the relationships between the electronic and the geometric structures for all known M3LxLyLz(mu-PR2)3 species. The basic stereochemical features are influenced by the total-electron count and, hence, by the degree of M-M bonding, as well as the remarkable flexibility of the phosphido bridging ligands. The mu-PR2 ligands need not necessarily lie in the M3 plane, and a wide range of M-P-M angles (as small as 72 degrees or as large as 133 degrees) have been observed.
Modification of Electrode Surfaces by Self-Assembled Monolayers of Thiol-Terminated Oligo(Phenyleneethynylene)s
Publisher: Wiley
Date: 11-01-2013
Abstract: The wire-like properties of four S-(4-{2-[4-(2-phenylethynyl)phenyl]ethynyl}phenyl) thioacetate derivatives, PhC≡CC(6)H(4)C≡CC(6)H(4)SAc (1), H(2)NC(6)H(4)C≡CC(6)H(4)C≡CC(6)H(4)SAc (2), PhC≡CC(6)H(2)(OMe)(2)C≡CC(6)H(4)SAc (3) and AcSC(6)H(4)C≡CC(6)H(4)C≡CC(6)H(4)SAc (4) (Figure 1), all of which possess a high degree of conjugation along the oligo(phenyleneethynylene) (OPE) backbone, were investigated as self-assembled monolayers (SAMs) on gold and platinum electrodes by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The redox probe [Fe(CN)(6)](4)(-) was used in both the CV and impedance experiments. The results indicate that the thiolates derived from thioacetate-protected precursor molecules 1 and 2 form well-ordered monolayers on a gold electrode, whereas SAMs derived from 3 and 4 exhibit randomly distributed pinholes. The electron tunnelling resistance and fractional coverage of SAMs of all four compounds were examined using electron tunnelling theory. The analysis of the results reveal that the well-ordered SAMs of 1 and 2 exhibit higher charge-transfer resistance in comparison to the defect-ridden SAMs of 3 and 4. The additional steric bulk offered by the methoxy groups in 3 is likely to prevent efficient packing within the SAM, leading to a microelectrode behaviour, when assembled on a gold electrode surface. The protected dithiol derivative 4 probably binds to the surface through both terminal groups which prevents dense packing and leads to the formation of a monolayer with randomly distributed pinholes. Atomic force microscopy (AFM) was used to examine the morphology of the monolayers, and height images gave root-mean-square (RMS) roughness's which are in agreement with the proposed SAM structures.
Synthetic and structural studies on C-ethynyl- and C-bromo-carboranes
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B517538K
Abstract: A high-yield preparation of the C-monoethynyl para-carborane, 1-Me(3)SiC[triple bond]C-1,12-C2B10H11, from C-monocopper para-carborane and 1-bromo-2-(trimethylsilyl)ethyne, BrC[triple bond]CSiMe(3) is reported. The low-yield preparation of 1,12-(Me3SiC[triple bond]C)2-1,12-C2B10H10 from the C,C'-dicopper para-carborane derivative with 1-bromo-2-(trimethylsilyl)ethyne, BrC[triple bond]CSiMe3, has been re-investigated and other products were identified including the C-monoethynyl-carborane 1-Me3SiC[triple bond]C-1,12-C2B10H11 and two-cage assemblies generated from cage-cage couplings. The contrast in the yields of the monoethynyl and diethynyl products is due to the highly unfavourable coupling process between 1-RC[triple bond]C-12-Cu-1,12-C2B10H10 and the bromoalkyne. The ethynyl group at the cage carbon C(1) strongly influences the chemical reactivity of the cage carbon at C(12)-the first ex le of the "antipodal effect" affecting the syntheses of para-carborane derivatives. New two-step preparations of 1-ethynyl- and 1,12-bis(ethynyl)-para-carboranes have been developed using a more readily prepared bromoethyne, 1-bromo-3-methyl-1-butyn-3-ol, BrC[triple bond]CCMe2OH. The molecular structures of the two C-monoethynyl-carboranes, 1-RC[triple bond]C-1,12-C2B10H11 (R = H and Me3Si), were experimentally determined using gas-phase electron diffraction (GED). For R = H (R(G) = 0.053) a model with C(5v) symmetry refined to give a C[triple bond]C bond distance of 1.233(5) A. For R = Me3Si (R(G) = 0.048) a model with C(s) symmetry refined to give a C[triple bond]C bond distance of 1.227(5) A. Molecular structures of 1,12-Br2-1,12-C2B10H10, 1-HC[triple bond]C-12-Br-1,12-C2B10H10 and 1,12-(Me(3)SiC[triple bond]C)2-1,12-C2B10H10 were determined by X-ray crystallography. Substituents at the cage carbon atoms on the C2B10 cage skeleton in 1-X-12-Y-1,12-C2B10H10 derivatives invariably lengthen the cage C-B bonds. However, the subtle substituent effects on the tropical B-B bond lengths in these compounds are more complex. The molecular structures of the ethynyl-ortho-carborane, 1-HC[triple bond]C-1,2-C2B10H11 and the ethene, trans-Me3SiBrC=CSiMe3Br are also reported.
The electronic structures of diruthenium complexes containing an oligo(phenylene ethynylene) bridging ligand, and some related molecular structures
Publisher: No publisher found
Date: 2010
DOI: 10.1039/C0DT00809E
Abstract: The complexes [{Cp'(L(2))Ru}C≡CC(6)H(4)C≡CC(6)H(2)(OMe)(2)C≡CC(6)H(4)C≡C{Ru(L(2))Cp'}](L(2) = (PPh(3))(2), Cp' = Cp L(2) = dppe, Cp' = Cp*) in which the metal centres are bridged by an oligomeric phenylene ethynylene (OPE) ligand have been prepared and the electronic structure of these representative ruthenium-capped OPEs investigated using a combination of electrochemical, UV-vis-NIR and IR spectroelectrochemical methods, and DFT-based calculations. The diruthenium complexes are oxidised to the thermodynamically stable dications [Cp'Ru(L(2))C≡CC(6)H(4)C≡CC(6)H(2)(OMe)(2)C≡CC(6)H(4)C≡CRu(L(2))Cp'](2+), which on the basis of the spectroelectrochemical and computational results can be described in terms of two non-interacting Ru(C≡CAr)(L(2))Cp' moieties. X-ray structures of the oligophenyleneethynylene HC≡CC(6)H(4)C≡CC(6)H(2)(OMe)(2)C≡CC(6)H(4)C≡CH, the bis(gold) complex Ph(3)PAuC≡CC(6)H(4)C≡CC(6)H(2)(OMe)(2)C≡CC(6)H(4)C≡CAuPPh(3) and the precursor 1-ethynyl-4-(trimethylsilylethynyl)benzene are also reported.
Transition Metal Complexes Containing All-Carbon Ligands
Publisher: Elsevier
Date: 2004
The use of scanning polarization force microscopy to study the miscibility of a molecular wire candidate and an insulating fatty acid in mixed LB films
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B716798A
Preparation of nascent molecular electronic devices from gold nanoparticles and terminal alkyne functionalised monolayer films
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4TC01080A
Abstract: A nascent metal–molecule–GNP assembly has been fabricated by immersion of a gold-substrate supported monolayer in a solution of gold nanoparticles (GNPs).
Redox Properties of Ferrocenyl Ene-diynyl-Bridged Cp*(dppe)M–C≡C–1,4-(C6H4) Complexes
Publisher: American Chemical Society (ACS)
Date: 26-10-2018
Preface: Professor Michael I. Bruce 65thBirthday Special Issue
Publisher: Springer Science and Business Media LLC
Date: 09-2004
Experimental and Theoretical Studies on Organic D‐π‐A Systems Containing Three‐Coordinate Boron Moieties as both π‐Donor and π‐Acceptor
Publisher: Wiley
Date: 30-12-2011
Abstract: Four linear π-conjugated systems with 1,3-diethyl-1,3,2-benzodiazaborolyl [C(6)H(4)(NEt)(2)B] as a π-donor at one end and dimesitylboryl (BMes(2)) as a π-acceptor at the other end were synthesized. These unusual push-pull systems contain phenylene (-1,4-C(6)H(4)- 1), biphenylene (-4,4'-(1,1'-C(6)H(4))(2)- 2), thiophene (-2,5-C(4)H(2)S- 3), and dithiophene (-5,5'-(2,2'-C(4)H(2)S)(2)- 4) as π-conjugated bridges and different types of three-coordinate boron moieties serving as both π-donor and π-acceptor. Molecular structures of 2, 3, and 4 were determined by single-crystal X-ray diffraction. Photophysical studies on these systems reveal blue-green fluorescence in all compounds. The Stokes shifts for 1, 2, and 3 are notably large at 7820-9760 cm(-1) in THF and 5430-6210 cm(-1) in cyclohexane, whereas the Stokes shift for 4 is significantly smaller at 5510 cm(-1) in THF and 2450 cm(-1) in cyclohexane. Calculations on model systems 1'-4' show the HOMO to be mainly diazaborolyl in character and the LUMO to be dominated by the empty p orbital at the boron atom of the BMes(2) group. However, there are considerable dithiophene bridge contributions to both orbitals in 4'. From the experimental data and MO calculations, the π-electron-donating strength of the 1,3-diethyl-1,3,2-benzodiazaborolyl group was found to lie between that of methoxy and dimethylamino groups. TD-DFT calculations on 1'-4', using B3LYP and CAM-B3LYP functionals, provide insight into the absorption and emission processes. B3LYP predicts that both the absorption and emission processes have strong charge-transfer character. CAM-B3LYP which, unlike B3LYP, contains the physics necessary to describe charge-transfer excitations, predicts only a limited amount of charge transfer upon absorption, but somewhat more upon emission. The excited-state (S(1)) geometries show the borolyl group to be significantly altered compared to the ground-state (S(0)) geometries. This borolyl group reorganization in the excited state is believed to be responsible for the large Stokes shifts in organic systems containing benzodiazaborolyl groups in these and related compounds.
The synthesis, molecular and electronic structure of cyanovinylidene complexes
Publisher: Elsevier BV
Date: 2012
Synthesis, Redox Chemistry, and Electronic Structure of the Butadiynyl and Hexatriynyl Complexes [Mo{(C≡C)nC≡CR}(L2)(η-C7H7)]z+ (
Publisher:
American Chemical Society (ACS)
Date:
14-08-2012
DOI:
10.1021/OM3005756
Publisher: American Chemical Society (ACS)
Date: 14-08-2012
DOI: 10.1021/OM3005756
Optical properties of donor–acceptor phenylene-ethynylene systems containing the 6-methylpyran-2-one group as an acceptor
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B502781K
Abstract: Donor-acceptor phenylene ethynylene systems containing the 6-methylpyran-2-one group, synthesized via classic or microwave-assisted Sonogashira cross-coupling, exhibit pronounced solvatochromism in fluorescence suggesting a highly polar excited state 4-[4-(4-N,N-dihexylaminophenylethynyl)phenylethynyl]-6-methylpyran-2-one has a fluorescence quantum yield >0.9 in cyclohexane.
The syntheses and structures of mono- and di-bromovinylidenes
Publisher: Elsevier BV
Date: 12-2009
Bis-Tridentate Iridium(III) Phosphors Bearing Functional 2-Phenyl-6-(imidazol-2-ylidene)pyridine and 2-(Pyrazol-3-yl)-6-phenylpyridine Chelates for Efficient OLEDs
Publisher: American Chemical Society (ACS)
Date: 19-05-2016
Bi- and polymetallic organometallics
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B514847M
Fabrication, Characterization, and Electrical Properties of Langmuir−Blodgett Films of an Acid Terminated Phenylene−Ethynylene Oligomer
Publisher: American Chemical Society (ACS)
Date: 10-02-2010
DOI: 10.1021/CM903270D
Towards the Fabrication of the Top‐Contact Electrode in Molecular Junctions by Photoreduction of a Metal Precursor
Publisher: Wiley
Date: 13-02-2014
Abstract: Langmuir films of 4-{[4-({4-[(trimethylsilyl)ethynyl]phenyl}ethynyl)phenyl]ethynyl} benzenaminium chloride ([1 H]Cl) undergo anion metathesis when assembled on an aqueous auric acid (HAuCl4 ) subphase. Subsequent transfer to solid supports gives well-formed Langmuir-Blodgett (LB) monolayers of [1 H]AuCl4 in which the trimethylsilyl group serves as the surface contacting group. Photoreduction of the aurate on these monolayers leads to the formation of metallic gold nanoislands, which were distributed over the surface of the film. Electrical properties of these nascent devices were determined by recording current-voltage (I-V) curves with conductive atomic force microscopy (c-AFM) using the PeakForce tunneling AFM (PF-TUNA) mode. This gives consistent sigmoidal I-V curves that are indicative of well-behaved junctions free of metallic filaments and short circuits. The photoreduction of a metal precursor incorporated onto monomolecular films is therefore proposed as an effective method for the fabrication of molecular junctions.
Towards a metallic top contact electrode in molecular electronic devices exhibiting a large surface coverage by photoreduction of silver cations
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6TC03319A
Abstract: Photoirradiation of monolayers incorporating a silver cation result in metal/monolayer/metal devices.
Reaction of a bis(bimetallic)-supported butadiyndiyl ligand with terminal acetylenes
Publisher: Springer Science and Business Media LLC
Date: 25-04-2007
Quantum Interference in Mixed-Valence Complexes: Tuning Electronic Coupling Through Substituent Effects.
Publisher: Wiley
Date: 11-10-2022
Abstract: Whilst 2- or 5-OMe groups on the bridging phenylene ring in [{Cp*(dppe)RuC≡C}
Palladium-catalyzed formation of secondary and tertiary amines from aryl dihalides with air-stable ferrocenyl tri- and diphosphines: Synthesis and X-ray structure of efficient catalysts beyond [PdCl2(
Publisher: Elsevier BV
Date: 06-2014
Towards the design of effective multipodal contacts for use in the construction of Langmuir–Blodgett films and molecular junctions
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9TC04710G
Abstract: The introduction of methylthioethers to the molecular wire 1,4-bis(pyridylethynyl)benzene gives rise to a prototypical one with a multipodal surface contacting motif that do not perturb the favourable electrical characteristics of the pyridyl group.
Electrically transmissive alkyne-anchored monolayers on gold
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8NR10464F
Abstract: Well-ordered, self-assembled monolayer films of 1,4-bis((4-ethynylphenyl)ethynyl)benzene on gold are shown to be nearly transparent to outer-sphere electron transfer processes.
Synthesis, spectroscopy and electronic structure of the vinylidene and alkynyl complexes [W(CCHR)(dppe)(η-C7H7)]+and [W(CCR)(dppe)(η-C7H7)]
Publisher:
Royal Society of Chemistry (RSC)
Date:
2011
DOI:
10.1039/C0DT01150A
Abstract: The first ex les of vinylidene complexes of the cycloheptatrienyl tungsten system [W(C=CHR)(dppe)(η-C₇H₇)](+) (dppe = Ph₂PCH₂CH₂PPh₂ R = H, 3 Ph, 4 C₆H₄-4-Me, 5) have been synthesised by reaction of [WBr(dppe)(η-C₇H₇)], 1, with terminal alkynes HC≡CR a one-pot synthesis of 1 from [WBr(CO)₂(η-C₇H₇)] facilitates its use as a precursor. The X-ray structure of 4[PF₆] reveals that the vinylidene ligand substituents lie in the pseudo mirror plane of the W(dppe)(η-C₇H₇) auxiliary (vertical orientation) with the phenyl group located syn to the cycloheptatrienyl ring. Variable temperature ¹H NMR investigations on [W(C=CH₂)(dppe)(η-C₇H₇)][PF₆], 3, estimate the energy barrier to rotation about the W=C(α) bond as 62.5 ± 2 kJ mol⁻¹ approximately 10 kJ mol⁻¹ greater than for the molybdenum analogue. Deprotonation of 4 and 5 with KOBu(t) yields the alkynyls [W(C≡CR)(dppe)(η-C₇H₇)] (R = Ph, 6 C₆H₄-4-Me, 7) which undergo a reversible one-electron oxidation at a glassy carbon electrode in CH₂Cl₂ with E(½) values approximately 0.12 V negative of Mo analogues. The 17-electron radicals [6](+) and [7](+) have been investigated by spectroelectrochemical IR, UV-visible and EPR methods. The electronic structures of representative vinylidene (3) and alkynyl (6) complexes have been investigated at the B3LYP/Def2-SVP level. In both cases, electronic structure is characterised by a frontier orbital with significant metal d(z²)character and this dominates the structural and spectroscopic properties of the system.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0DT01150A
Abstract: The first ex les of vinylidene complexes of the cycloheptatrienyl tungsten system [W(C=CHR)(dppe)(η-C₇H₇)](+) (dppe = Ph₂PCH₂CH₂PPh₂ R = H, 3 Ph, 4 C₆H₄-4-Me, 5) have been synthesised by reaction of [WBr(dppe)(η-C₇H₇)], 1, with terminal alkynes HC≡CR a one-pot synthesis of 1 from [WBr(CO)₂(η-C₇H₇)] facilitates its use as a precursor. The X-ray structure of 4[PF₆] reveals that the vinylidene ligand substituents lie in the pseudo mirror plane of the W(dppe)(η-C₇H₇) auxiliary (vertical orientation) with the phenyl group located syn to the cycloheptatrienyl ring. Variable temperature ¹H NMR investigations on [W(C=CH₂)(dppe)(η-C₇H₇)][PF₆], 3, estimate the energy barrier to rotation about the W=C(α) bond as 62.5 ± 2 kJ mol⁻¹ approximately 10 kJ mol⁻¹ greater than for the molybdenum analogue. Deprotonation of 4 and 5 with KOBu(t) yields the alkynyls [W(C≡CR)(dppe)(η-C₇H₇)] (R = Ph, 6 C₆H₄-4-Me, 7) which undergo a reversible one-electron oxidation at a glassy carbon electrode in CH₂Cl₂ with E(½) values approximately 0.12 V negative of Mo analogues. The 17-electron radicals [6](+) and [7](+) have been investigated by spectroelectrochemical IR, UV-visible and EPR methods. The electronic structures of representative vinylidene (3) and alkynyl (6) complexes have been investigated at the B3LYP/Def2-SVP level. In both cases, electronic structure is characterised by a frontier orbital with significant metal d(z²)character and this dominates the structural and spectroscopic properties of the system.
Synthesis, characterisation and application of lanthanide cyclen complexes in organic synthesis
Publisher: Royal Society of Chemistry (RSC)
Date: 04-03-2002
DOI: 10.1039/B111628B
Self-Assembled Molecular Wires from Organoiron Metalloligands and Ruthenium Tetramesitylporphyrin
Publisher: American Chemical Society (ACS)
Date: 23-09-2010
DOI: 10.1021/IC1012445
Abstract: A trinuclear assembly of two (η(2)-dppe)(η(5)-C(5)Me(5))FeC≡C(4-Py) (Py = pyridyl) metalloligands apically coordinated to a ruthenium(II) tetramesitylporphyrin is demonstrated to behave as a molecular wire in the monooxidized state.
Fabrication of metallic and non-metallic top electrodes for large-area molecular junctions
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1NR00917F
Abstract: This Review presents an overview of methods used to deposit top-contact electrodes on electrode-supported monolayers to create ‘large area’ molecular junctions, highlighting the challenges and solutions identified to date.
Alkynyl-Phosphine Substituted Fe2S2 Clusters: Synthesis, Structure and Spectroelectrochemical Characterization of a Cluster with a Class III Mixed-Valence [FeFe]3+ Core
Publisher: Springer Science and Business Media LLC
Date: 05-09-2014
Tetrakis(ferrocenylethynyl)ethene: Synthesis, (Spectro)electrochemical and quantum chemical characterisation
Publisher: Elsevier BV
Date: 10-2016
Solvent Dependence of the Single Molecule Conductance of Oligoyne-Based Molecular Wires
Publisher: American Chemical Society (ACS)
Date: 28-12-2015
Electron Delocalization in Reduced Forms of 2-(BMes2)pyrene and 2,7-Bis(BMes2)pyrene
Publisher: American Chemical Society (ACS)
Date: 22-05-2015
DOI: 10.1021/JACS.5B03805
Abstract: Reduction of 2-(BMes2)pyrene (B1) and 2,7-bis(BMes2)pyrene (B2) gives rise to anions with extensive delocalization over the pyrenylene bridge and between the boron centers at the 2- and 2,7-positions, the typically unconjugated sites in the pyrene framework. One-electron reduction of B2 gives a radical anion with a centrosymmetric semiquinoidal structure, while two-electron reduction produces a quinoidal singlet dianion with biradicaloid character and a relatively large S0-T1 gap. These results have been confirmed by cyclic voltammetry, X-ray crystallography, DFT/CASSCF calculations, NMR, EPR, and UV-vis-NIR spectroscopy.
Reaction of {Ru(PPh3)2Cp}2(μ-C4) with tetracyanoethene: macrocycle formation by intermolecular CN coordination
Publisher: Royal Society of Chemistry (RSC)
Date: 1998
DOI: 10.1039/A709202D
Heterometallic complexes containing C4 chains. X-ray structures of {Cp(OC)3W}C≡CC≡C{Ir(CO)(PPh3)2(O2)} and cis-Pt{C≡CC≡C[W(CO)3Cp]}2(PEt3)2
Publisher: Elsevier BV
Date: 04-2000
Turning the Tap: Conformational Control of Quantum Interference to Modulate Single‐Molecule Conductance
Publisher: Wiley
Date: 31-10-2019
Abstract: Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum‐interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular‐design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta ‐substituted phenylene ethylene‐type oligomers ( m ‐OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular‐scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic‐ratio and orbital‐product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single‐molecule devices with desirable electronic functions.
Potential‐Modulated Ion Distributions in the Back‐to‐Back Electrical Double Layers at a Polarised Liquid|Liquid Interface Regulate the Kinetics of Interfacial Electron Transfer
Publisher: Wiley
Date: 27-12-2022
Abstract: Biphasic interfacial electron transfer (IET) reactions at polarisable liquid|liquid (L|L) interfaces underpin new approaches to electrosynthesis, redox electrocatalysis, bioelectrochemistry and artificial photosynthesis. Herein, using cyclic and alternating current voltammetry, we demonstrate that under certain experimental conditions, the biphasic 2‐electron O 2 reduction reaction can proceed by single‐step IET between a reductant in the organic phase, decamethylferrocene, and interfacial protons in the presence of O 2 . Using this biphasic system, we demonstrate that the applied interfacial Galvani potential difference provides no direct driving force to realise a thermodynamically uphill biphasic IET reaction in the mixed solvent region. We show that the onset potential for a biphasic single‐step IET reaction does not correlate with the thermodynamically predicted standard Galvani IET potential and is instead closely correlated with the potential of zero charge at a polarised L|L interface. We outline that the applied required to modulate the interfacial ion distributions, and thus kinetics of IET, must be optimised to ensure that the aqueous and organic redox species are present in substantial concentrations at the L|L interface simultaneously in order to react.
Biodegradable Materials and Green Processing for Green Electronics
Publisher: No publisher found
Date: 2020
The syntheses, structures and spectroelectrochemical properties of 6-oxo-verdazyl derivatives bearing surface anchoring groups
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1TC05495C
Abstract: The electronic properties of 6-oxo-verdazyl radicals are tuned by substituents at the 1- and 5-positions, with frontier orbital analysis indicating that each system should display constructive quantum interference in a molecular junction.
Understanding the charge transport properties of redox active metal–organic conjugated wires
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7SC04727D
Abstract: For Rh 2 -organic molecular wires, we found that weaker coupling systems built using longer bridging ligands exhibit better electrical conductance.
19 Organometallic chemistry of bi- and polymetallic complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B410479J
Cover Feature: Potential‐Modulated Ion Distributions in the Back‐to‐Back Electrical Double Layers at a Polarised Liquid|Liquid Interface Regulate the Kinetics of Interfacial Electron Transfer (ChemEle
Publisher: Wiley
Date: 23-01-2023
Noninnocent Ligand Behavior in Diruthenium Complexes Containing a 1,3-Diethynylbenzene Bridge
Publisher: American Chemical Society (ACS)
Date: 10-08-2009
DOI: 10.1021/OM900200N
Excited State Mixed‐Valence Complexes: From the Special Pair to the Creutz–Taube Ion and Beyond
Publisher: Wiley
Date: 08-02-2023
Abstract: Compounds and complexes with mixed‐valence electronic ground states, such as the Creutz–Taube ion, have proven to be excellent vehicles through which to study intramolecular electron‐transfer processes. In a recent contribution by Cadranel and co‐workers, time‐resolved pump‐probe spectroscopy reveals photo‐induced metal‐to‐bridge charge transfer within the homovalent analogue of the Creutz–Taube ion, [{(NH 3 ) 5 Ru}(μ‐pz){Ru(NH 3 ) 5 }] 4+ , giving rise to two closely lying excited states with mixed‐valence character, one with a shorter lifetime ( τ =136 ps) and weakly‐coupled (Robin‐Day Class II) character, the other a longer‐lived ( τ =2.8 ns) configurational isomer with more delocalized electronic structure. Electron transfer reactions from the longer‐lived species demonstrate analogies with the photo‐induced reactions of the photosynthetic special pair, suggesting this state as a reference system for excited state mixed‐valency, and a framework from which to explore photocatalytic reactions.
Combined Spectroscopic and Quantum Chemical Study of [trans-Ru(C≡CC6H4R1-4)2(dppe)2]n+ and [trans-Ru(C≡CC6
Publisher:
American Chemical Society (ACS)
Date:
18-09-1970
DOI:
10.1021/OM500265S
The synthesis and liquid crystalline behaviour of alkoxy‐substituted derivatives of 1,4‐bis(phenylethynyl)benzene
Publisher: Informa UK Limited
Date: 02-2008
Synthesis, Redox Chemistry, and Electronic Structure of the Alkynyl Cyclopentadienyl Molybdenum Complexes [Mo(C≡CR)(CO)(L2)Cp′]n+ (n = 0 or 1; R = Ph or C6
Publisher:
American Chemical Society (ACS)
Date:
28-06-2011
DOI:
10.1021/OM200229C
Ligand redox non-innocent behaviour in ruthenium complexes of ethynyl tolans
Publisher: Elsevier BV
Date: 08-2011
Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(µ-CCCC)]
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B712104K
Abstract: The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os([=C=CH2)(dppe)Cp*]PF6 ([11]PF6), [Os(C triple bond CH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{mu-(=C=CH-CH=C=)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}(2)(mu-C triple bond CC triple bond C)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(mu-C triple bond CC triple bond C)] (M = Fe, Ru, Os). The molecular structures of []PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(C triple bond CPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe approximately Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(mu-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.
Substitution of Tetracyanoethene by Ethynyl–Metal Complexes Gives Tricyanovinylethynyl (Tricyanobutenynyl) Derivatives: Syntheses, Protonation, and Addition of Metal–Ligand Fragments
Publisher: American Chemical Society (ACS)
Date: 11-2011
DOI: 10.1021/OM2007503
The molecular structures and electrochemical response of “twisted” tetra(aryl)benzidenes
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B404731A
Synthesis and structure of metallocarbon clusters bearing pendant ethynyl ligands. X-ray crystal structures of Os3(CO)9(μ-CO)(μ3-η1,η1,η2-Me3SiCCC2CCSiMe3), Os3Ru(CO)12(μ4-η1,η2,η1,η2-Me3SiCCC2CCS
Publisher: Elsevier BV
Date: 04-1999
Rapid and sensitive colorimetric sensing of the insecticide pymetrozine using melamine-modified gold nanoparticles
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7AY02658G
Abstract: A rapid, selective, visual detection sensor with high sensitivity and low detection limits for the pesticide pymetrozine (PYM) was prepared from melamine-modified gold nanoparticles (M-Au NPs), and shown to be effective in both natural water and food s les.
Syntheses, structural characterisation and electronic structures of some simple acyclic amino carbene complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT01806D
Abstract: Reactions of the vinylidene complexes [M(CCH 2 )(PP)Cp′]PF 6 with NH 3 readily afford the acyclic amino carbene complexes [M{C(Me)NH 2 }(PP)Cp′]PF 6 [M(PP)Cp′ = Fe(dppe)Cp, Ru(dppe)Cp, Ru(PPh 3 ) 2 Cp, Ru(dppe)Cp*].
Electronic Interactions Between and Through Covalently-Bonded Polymetallic Complexes
Publisher: Springer Science and Business Media LLC
Date: 25-05-2010
Rational Control of Conformational Distributions and Mixed-Valence Characteristics in Diruthenium Complexes.
Publisher: Wiley
Date: 04-10-2016
Abstract: The electronic characteristics of mixed-valence complexes are often inferred from the shape of the inter-valence charge transfer (IVCT) band, which usually falls in the near infrared (NIR) region, and relationships derived from Marcus-Hush theory. These analyses typically assume one single, dominant molecular conformation. The NIR spectra of the prototypical delocalised (Class III Robin-Day mixed-valence) complexes [{Ru(pp)Cp'}
Iron versus Ruthenium: Dramatic Changes in Electronic Structure Result from Replacement of One Fe by Ru in [{Cp*(dppe)Fe}-CC-CC-{Fe(dppe)Cp*}]n+ (n = 0, 1, 2)
Publisher: American Chemical Society (ACS)
Date: 07-2005
DOI: 10.1021/OM050293A
Metal complexes in molecular electronics: progress and possibilities
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B506017F
Abstract: A selective summary of some of the issues surrounding the development of a molecular-based electronics technology is presented, highlighting the characteristics of metal complexes that make these species particularly attractive for the construction of highly integrated, functional molecular components.
Some reactions of an η3-tetracyanobutadienyl-ruthenium complex
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B921324D
Abstract: In the eta(3)-butadienyl complex Ru{eta(3)-C(CN)(2)CPhC=C(CN)(2)}(PPh(3))Cp 1, which is formed from Ru(C[triple bond]CPh)(PPh(3))(2)Cp and tcne, a CN group reacts with MeO(-) to give the methoxy-amide Ru{NH=C(OMe)C(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 2, in which the NH has displaced the C=C from the Ru centre with formation of a RuC(3)N ring. "Click addition" of azide to a CN group in 1 gives the oligomeric tetrazolato complex Ru{N(3)N[Na(OEt(2))]=CC(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 3, also containing a RuC(3)N ring. Salt-elimination reactions of 3 with MeOTf, FeCl(dppe)Cp, RuCl(dppe)Cp* and trans-PtCl(2){P(tol)(3)}(2) result in selective substitution at one nitrogen atom of the RuC(3)N ring. Geometries of 1 and the anion in 3 were computed by DFT methods. Preferences for CN groups attacked in the nucleophilic and cycloaddition reactions of 1 are supported by NBO calculations. Alkylation of 1 in reactions with 1,2-dimethoxyethane gave two isomers of Ru{N(3)[CH(CH(2)OMe)(OMe)]N=CC(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 8 and 9, differing in the sites of attachment of the alkyl group, likely by radical processes. The molecular structures of eight complexes are reported, including a re-determination of 1. Computed NMR chemical shifts are used to reassign the butadienyl carbon resonances in the (13)C NMR spectrum of 1.
Single‐Molecule Conductance Studies of Organometallic Complexes Bearing 3‐Thienyl Contacting Groups
Publisher: Wiley
Date: 16-01-2017
Preparation of Ordered Films Containing a Phenylene Ethynylene Oligomer by the Langmuir−Blodgett Technique
Publisher: American Chemical Society (ACS)
Date: 06-2007
DOI: 10.1021/JP072052H
Abstract: This paper reports the fabrication and characterization of Langmuir and Langmuir-Blodgett (LB) films incorporating an oligo(phenylene-ethynylene) (OPE) derivative, namely, 4-[4-(4-hexyloxyphenylethynyl)-phenylethynyl]-benzoic acid (HBPEB). Conditions appropriate for deposition of monolayers of HBPEB at the air-water interface have been established and the resulting Langmuir films characterized by a combination of surface pressure and surface potential versus area per molecule isotherms, Brewster angle microscopy, and ultraviolet reflection spectroscopy. The Langmuir films are readily transferred onto solid substrates, and one-layer LB films transferred at several surface pressures onto mica substrates have been analyzed by means of atomic force microscopy, from which it can be concluded that 14 mN/m is an optimum surface pressure of transference, giving well-ordered homogeneous films without three-dimensional defects and a low surface roughness. The optical and emissive properties of the LB films have been determined with significant blue-shifted absorption spectra indicating formation of two-dimensional H aggregates and a Stokes shift illustrating the effects of the solid-like environment on the molecular chromophore.
Characterization and Conductivity of Langmuir–Blodgett Films Prepared from an Amine-Substituted Oligo(phenylene ethynylene)
Publisher: American Chemical Society (ACS)
Date: 06-12-2007
DOI: 10.1021/CM702532M
Electronic structure and spectroscopy of the cycloheptatrienyl molybdenum halide complexes [MoBrL2(η-C7H7)]+ (L2= 2CO, n= 0; L2= 2,2′-bipyridyl, n= 0 or 1)
Publisher: Elsevier BV
Date: 2015
Metal-stabilised diynyl radicals: structure and reactivity of [Mo(CC–CCSiMe3)L2(η-C7H7)]˙+ (L2 = 2,2′-bipyridine or dppe)
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B924759A
Abstract: The unprecedented spectroscopic and structural characterisation of a series of 17-electron, monometallic diynyl radicals, [Mo(C[triple bond]C-C[triple bond]CR)L(2)(eta-C(7)H(7))]*(+) (L(2) = bipy, R = SiMe(3) L(2) = dppe, R = SiMe(3) or H), are reported the (L(2) = dppe, R = SiMe(3)) derivative is reactive to chain-centred C(beta)-C(beta') dimerisation.
4,4′-Diamino-2,2′,6,6′-tetramethylbiphenyl
Publisher: International Union of Crystallography (IUCr)
Date: 23-06-2006
DOI: 10.1107/S1600536806022756
Abstract: Each of the three independent molecules of the title compound, C 16 H 20 N 2 , has near-perpendicular benzene rings and pyramidal N atoms. Hydrogen bonding in the structure is rather inefficient.
Chiral NH-Controlled Supramolecular Metallacycles
Publisher: American Chemical Society (ACS)
Date: 20-01-2017
DOI: 10.1021/JACS.6B11422
Abstract: Chiral NH functionalities-based discrimination is a key feature of Nature's chemical armory, yet selective binding of biologically active molecules in synthetic systems with high enantioselectivity poses significant challenges. Here we report the assembly of three chiral fluorescent Zn
Transition Metal Chemistry of 1,3-Diynes, Poly-ynes, and Related Compounds
Publisher: Elsevier
Date: 2001
Towards molecular electronic devices based on 'all-carbon' wires.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8NR02347F
Abstract: Nascent molecular electronic devices based on linear 'all-carbon' wires attached to gold electrodes through robust and reliable C-Au contacts are prepared via efficient in situ sequential cleavage of trimethylsilyl end groups from an oligoyne, Me
A Combined Spectroelectrochemical and Computational Study of the Chemically Reversible 2-Electron Reduction of [Ru4(μ-RC2R)2(CO)11] Clusters
Publisher: American Chemical Society (ACS)
Date: 15-02-2005
DOI: 10.1021/OM049457Y
Synthesis and structure of a series of tungsten(ii) and tungsten(vi) diynyl and diyndiyl complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 11-02-2003
DOI: 10.1039/B212074G
Molybdenum Complexes of C,C-Bis(ethynyl)carboranes: Design, Synthesis, and Study of a Weakly Coupled Mixed-Valence Compound
Publisher: American Chemical Society (ACS)
Date: 31-12-2010
DOI: 10.1021/OM1010353
The Use of Bridging Ligand Substituents to Bias the Population of Localized and Delocalized Mixed‐Valence Conformers in Solution
Publisher: Wiley
Date: 23-06-2022
Abstract: The electronic structure and associated spectroscopic properties of ligand‐bridged, bimetallic ‘mixed‐valence’ complexes of the general form {M}(μ‐B){M + } are dictated by the electronic couplings, and hence orbital overlaps, between the metal centers mediated by the bridge. In the case of complexes such as [{Cp*(dppe)Ru}(μ‐C≡CC 6 H 4 C≡C){Ru(dppe)Cp*}] + , the low barrier to rotation of the half‐sandwich metal fragments and the arylene bridge around the acetylene moieties results in population of many energy minima across the conformational energy landscape. Since orbital overlap is also sensitive to the particular mutual orientations of the metal fragment(s) and arylene bridge through a Karplus‐like relationship, the different members of the population range exemplify electronic structures ranging from strongly localized (weakly coupled Robin‐Day Class II) to completely delocalized (Robin‐Day Class III). Here, we use electronic structure calculations with the hybrid density functional BLYP35‐D3 and a continuum solvent model in combination with UV‐vis‐NIR and IR spectroelectrochemical studies to show that the conformational population in complexes [{Cp*(dppe)Ru}(μ‐C≡CArC≡C){Ru(dppe)Cp*] + , and hence the dominant electronic structure, can be biased through the steric and electronic properties of the diethynylarylene (Ar) moiety (Ar=1,4‐C 6 H 4 , 1,4‐C 6 F 4 , 1,4‐C 6 H 2 ‐2,5‐Me 2 , 1,4‐C 6 H 2 ‐2,5‐(CF 3 ) 2 , 1,4‐C 6 H 2 ‐2,5‐ i Pr 2 ).
Cavity Ring-Down Spectroscopy of the Torsional Motions of 1,4-Bis(phenylethynyl)benzene
Publisher: American Chemical Society (ACS)
Date: 21-01-2006
DOI: 10.1021/JP054426H
Abstract: The torsional motions of jet-cooled 1,4-bis(phenylethynyl)benzene (BPEB), a prototype molecular wire, were studied using cavity ring-down spectroscopy in the first UV absorption band (316-321 nm). The torsional spectrum of 1,4-bis(phenylethynyl)-2,3,5,6-tetradeuteriobenzene was also recorded in the gas phase. Both spectra were successfully simulated using simple cosine potentials to describe the torsional motions. The ground-state barrier to rotation was estimated to be 220-235 cm(-1), which is similar to that of diphenylacetylene (tolane). Complementary DFT calculations were found to overestimate the torsional barrier.
Electrochemical studies of bi- and polymetallic complexes featuring acetylide based bridging ligands
Publisher: Springer Science and Business Media LLC
Date: 28-09-2005
A Spectroscopic and Computationally Minimal Approach to the Analysis of Charge‐Transfer Processes in Conformationally Fluxional Mixed‐Valence and Heterobimetallic Complexes
Publisher: Wiley
Date: 05-06-2019
Abstract: Class II mixed-valence bimetallic complexes {[Cp'(PP)M]C≡C-C≡N[M'(PP)'Cp']}
Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te
Publisher: Wiley
Date: 21-11-2017
Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum
Publisher: Wiley
Date: 16-04-2014
Redox-Active Complexes Containing Group 8 Metal Centers Linked by C2 Bridges
Publisher: American Chemical Society (ACS)
Date: 21-06-2007
DOI: 10.1021/OM7002859
Reactions of alkynes with cis-RuCl2(dppm)2: exploring the interplay of vinylidene, alkynyl and η3-butenynyl complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT03844H
Abstract: The course of reactions between cis -RuCl 2 (dppm) 2 and terminal alkynes is shown to depend markedly on the electronic character of the alkyne reagent.
Alkenylvinylidene and allenylidene complexes: evidence for the formation of a metal–trienylidene intermediate
Publisher: Royal Society of Chemistry (RSC)
Date: 1996
DOI: 10.1039/CC9960001009
Syntheses and Chemistry of the Diynyl Complexes M(C⋮CC⋮CH)(CO)3(η-C5H5) (M = Mo, W): Crystal Structures of W(C⋮CC⋮CSiMe3)(CO)3(η-C5H<
Publisher: American Chemical Society (ACS)
Date: 10-07-1998
DOI: 10.1021/OM980031R
Syntheses and Structures of trans‐bis(Alkenylacetylide) Ruthenium Complexes
Publisher: Wiley
Date: 14-09-2021
Abstract: A series of ruthenium alkenylacetylide complexes trans‐ [Ru{C≡CC(=CH 2 )R}Cl(dppe) 2 ] (R=Ph ( 1 a ), c C 4 H 3 S ( 1 b ), 4‐MeS‐C 6 H 4 ( 1 c ), 3,3‐dimethyl‐2,3‐dihydrobenzo[ b ]thiophene (DMBT) ( 1 d )) or trans‐ [Ru{C≡C‐ c C 6 H 9 }Cl(dppe) 2 ] ( 1 e ) were allowed to react with the corresponding propargylic alcohol HC≡CC(Me)R(OH) (R=Ph ( A ), c C 4 H 3 S ( B ), 4‐MeS‐C 6 H 4 ( C ), DMBT ( D ) or HC≡C‐ c C 6 H 10 (OH) ( E ) in the presence of TlBF 4 and DBU to presumably give alkenylacetylide/allenylidene intermediates trans‐ [Ru{C≡CC(=CH 2 )R}{C=C=C(Me)}(dppe) 2 ]PF 6 ([ 2 ]PF 6 ). These complexes were not isolated but deprotonated to give the isolable bis(alkenylacetylide) complexes trans‐ [Ru{C≡CC(=CH 2 )R} 2 (dppe) 2 ] (R=Ph ( 3 a ), c C 4 H 3 S ( 3 b ), 4‐MeS‐C 6 H 4 ( 3 c ), DMBT ( 3 d )) and trans‐ [Ru{C≡C‐ c C 6 H 9 } 2 (dppe) 2 ] ( 3 e ). Analogous reactions of trans‐ [Ru(CH 3 ) 2 (dmpe) 2 ], featuring the more electron‐donating 1,2‐bis(dimethylphosphino)ethane (dmpe) ancillary ligands, with the propargylic alcohols A or C and NH 4 PF 6 in methanol allowed isolation of the intermediate mixed alkenylacetylide/allenylidene complexes trans‐ [Ru{C≡CC(=CH 2 )R}{C=C=C(Me)}(dmpe) 2 ]PF 6 (R=Ph ([ 4 a ]PF 6 ), 4‐MeS‐C 6 H 4 ([ 4 c ]PF 6 ). Deprotonation of [ 4 a ]PF 6 or [ 4 c ]PF 6 gave the symmetric bis(alkenylacetylide) complexes trans‐ [Ru{C≡CC(=CH 2 )R} 2 (dmpe) 2 ] (R=Ph ( 5 a ), 4‐MeS‐C 6 H 4 ( 5 c )), the first of their kind containing the dmpe ancillary ligand sphere. Attempts to isolate bis(allenylidene) complexes [Ru{C=C=C(Me)R} 2 (PP) 2 ] 2+ (PP=dppe, dmpe) from treatment of the bis(alkenylacetylide) species 3 or 5 with HBF 4 ⋅ Et 2 O were ultimately unsuccessful.
Electrochemically grafted single molecule junctions exploiting a chemical protection strategy
Publisher: Elsevier BV
Date: 12-2016
Optical Behaviors and Electronic Properties of Mo2–Mo2 Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model
Publisher: American Chemical Society (ACS)
Date: 07-12-2017
A Safe and Simple Synthesis of 1,4-Bis(trimethylsilyl)buta-1,3-diyne
Publisher: CSIRO Publishing
Date: 2018
DOI: 10.1071/CH17402
Abstract: The buta-1,3-diyne synthon 1,4-bis(trimethylsilyl)buta-1,3-diyne (1) is an important building block for the introduction of butadiyne motifs into organic and organometallic structures. Although 1 is commonly prepared from the Hay homo-coupling of trimethylsilylacetylene (catalytic CuI/tetramethylethynylenediamine, O2, acetone), the report of a significant explosion during this preparation, likely arising from a static discharge during addition of the catalyst solution to the alkyne/acetone/O2 rich atmosphere, prompts consideration of alternative procedures. Here we report the use of the robust Navale catalyst system (CuI/N,N-dimethylaminopyridine, O2, NCMe) in the multigram-scale preparation of 1 with minimal manipulation of all-glass apparatus, greatly simplifying the process and minimising risks associated with the preparation of this useful compound.
Some reactions of the ruthenium allenylidene complex [Ru(CCCPh2)(PPh3)2Cp][PF6] with nucleophiles
Publisher: Elsevier BV
Date: 1999
Trimetallic complexes featuring Group 10 tetracyanometallate dianions as bridging ligands
Publisher: Elsevier BV
Date: 08-2006
Twists and turns: Studies of the complexes and properties of bimetallic complexes featuring phenylene ethynylene and related bridging ligands
Publisher: Elsevier BV
Date: 05-2013
The structure and coordinative self-assembly of films based on a palladium compound of pyridyl-acetylene platinum and its application in Suzuki and Heck coupling reactions
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3TA11868A
Cyanoacetylenes and cyanoacetylides: versatile ligands in organometallic chemistry
Publisher: Royal Society of Chemistry (RSC)
Date: 2003
DOI: 10.1039/B306089F
Synthesis, Characterization, Electrochemistry, and Computational Studies of Ferrocenyl-Substituted Siloles
Publisher: American Chemical Society (ACS)
Date: 27-03-2014
DOI: 10.1021/OM500072Q
Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT00758E
Abstract: An investigation of C -dimesitylboryl- ortho -carboranes, 1-(BMes 2 )-2-R-1,2-C 2 B 10 H 10 ( 1 and 2 ), reveals that the carborane is the electron-acceptor and the mesityl group is the electron-donor in these dyads.
Professor Ken Wade, F.R.S. 13th October 1932–16th March 2014
Publisher: Springer Science and Business Media LLC
Date: 26-06-2014
Spectroscopic Evidence for Redox Isomerism in the 1,4-Diethynylbenzene-Bridged Heterobimetallic Cation [{Fe(dppe)Cp*}(μ-C≡CC6H4C≡C){Mo(dppe)(η-C7H7)}]PF
Publisher:
American Chemical Society (ACS)
Date:
08-07-2011
DOI:
10.1021/OM200488B
Publisher: American Chemical Society (ACS)
Date: 08-07-2011
DOI: 10.1021/OM200488B
Syntheses and molecular structures of some tricobaltcarbonylclusters containing 2,4,6-trimethyl-1,3,5-trithiane
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B909708B
Abstract: Reactions of CCo3 carbonyl clusters Co3(mu3-CR)(CO)9 with 2,4,6-trimethyl-1,3,5-trithiane (SMe3) have given Co3(mu3-CR)(mu3-SMe3)(CO)6 [R = H (1), C[triple bond]CSiMe3 (2)]. A small amount of the coupled-alkyne product Me3SiC2[Co2(CO)6]C2[Co2(mu-SMe3)(CO)4]C[triple bond]CSiMe3 (3) was isolated from the latter reaction. The reaction of Co3(mu3-CC[triple bond]CSiMe3)(mu3-SMe3)(CO)6 (2) with AuCl(PPh3) in the presence of NaOMe gave Co3{mu3-CC[triple bond]CAu(PPh3)}(mu3-SMe3)(CO)6 (4), which in turn reacts with Co3(mu3-CBr)(CO)9 in the presence of catalytic amounts of Pd(PPh3)4 and CuI to give {(OC)9Co3}(mu-C[triple bond]CC[triple bond]C){Co3(mu3-SMe3)(CO)6} (5). Further substitution of 5 with SMe3 gave symmetrical {Co3(mu3-SMe3)(CO)6}2(mu-C[triple bond]CC[triple bond]C) (6), also obtained from a reaction between {Co3(CO)9}2(mu-C[triple bond]CC[triple bond]C) and two equivalents of SMe3. Similar substitution of Co3{mu3-C(C[triple bond]C)2[Ru(dppe)Cp*]}(CO)9 with SMe3 gave Co3{mu3-C(C[triple bond]C)2[Ru(dppe)Cp*]}(mu3-SMe3)(CO)6 (7). In all of these compounds, the SMe3 ligand caps the basal face of the CCo3 cluster on the opposite side to the mu3-CR group. The three S donors occupy axial sites, with all CO groups being in equatorial sites. Reactions of Co3(mu3-CBr)(CO)9 with SMe3 gave only Co3(mu3-CX)(mu3-SMe3)(CO)6 [X = C(O)NMe2 (8), CO2H (9)]. The redox properties and electronic structure of the C4-bridged bis-cluster 6 have been investigated through a combination of cyclic voltammetry, IR spectroelectrochemistry and DFT calculations, with comparisons made with suitable model systems. Single-crystal X-ray diffraction structure determinations of 1, 2, 3, 4 and 8 are reported.
21 Organometallic chemistry of bi- and poly-nuclear complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2002
DOI: 10.1039/B109671K
1,6-Bis(trimethylsilyl)hexa-1,3,5-triyne as a precursor to ruthenium clusters containing highly ethynylated ligands
Publisher: Elsevier BV
Date: 08-1998
A simple synthesis of tetraethynylethenes and representative molecular structures of some dicobalt derivatives
Publisher: Elsevier BV
Date: 03-2003
Synthesis of new mer,trans-rhodium(III) hydrido-bis(acetylide) complexes: Structure of mer,trans-[(PMe3)3Rh(CC–C6H4-4-NMe2)2H]
Publisher: Elsevier BV
Date: 06-2006
Syntheses and reactions of some cluster complexes containing C4 ligands with iron, ruthenium and cobalt carbonyls
Publisher: Royal Society of Chemistry (RSC)
Date: 2000
DOI: 10.1039/B002406F
A Combined Computational and Spectroelectrochemical Study of Platinum-Bridged Bis-Triarylamine Systems
Publisher: American Chemical Society (ACS)
Date: 22-01-2014
DOI: 10.1021/IC402538E
Abstract: The character of the electronic transitions in the ultraviolet-visible-near infrared (UV-vis-NIR) spectra of platinum-bis(alkynyl) bridged, bis-triarylamine mixed-valence systems trans-[Pt(C≡CC6H4NAr2)2 (PR3)2](n+) (R = ethyl, Ar = C6H4CH3-4 (1) or C6H4OCH3-4 (2) R = Ph, Ar = C6H4CH3-4 (3) or C6H4OCH3-4 (4), n = 0, 1, 2) has been determined from a combination of spectroscopic measurement and density functional theory calculations. The hybrid functional BLYP35 in combination with a suitable solvent model (i.e., conductor-like screening model (COSMO)) has been used to model the UV-vis-NIR and IR spectroscopic properties of [1-4](+), to confirm the description of [1-4](+) as ex les of metal-bridged organic mixed-valence compounds, and to assign the principal features of the electronic spectra, including the triarylamine-based intervalence charge transfer transition located in the NIR region. The successful modeling of the charge distribution within the system demonstrates the utility of the BLYP35-COSMO protocol as a tool for use in the study of intramolecular charge transfer properties in mixed-valence complexes.
Straightforward Access to Tetrametallic Complexes with a Square Array by Oxidative Dimerization of Organometallic Wires
Publisher: American Chemical Society (ACS)
Date: 30-05-2013
DOI: 10.1021/OM4003768
Polycarbon Ligand Chemistry: Electronic Interactions between a Mononuclear Ruthenium Fragment and a Cobalt−Carbon Cluster Core
Publisher: American Chemical Society (ACS)
Date: 09-1999
DOI: 10.1021/OM990290W
Carborane radical anions: spectroscopic and electronic properties of a carborane radical anion with a 2n + 3 skeletal electron count
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B700110J
Abstract: One-electron reduction of the well-known carborane 1,2-Ph2-1,2-C2B10H10 (1) gives rise to a stable carborane radical anion ([1]-) with a true 2n + 3 cluster electron count the geometry of ([1]-) features an elongated C...C cage distance but no significant pi-bonding interactions between the cage and the phenyl substituents.
Enhanced bi-stability in a ruthenium alkynyl spiropyran complex
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT01107H
Abstract: Attachment of a ruthenium alkynyl unit to a spiropyran ligand extends the lifetime of the merocyanine form of the complex more than twenty-fold.
Metal–Molecule–Metal Junctions in Langmuir–Blodgett Films Using a New Linker: Trimethylsilane
Publisher: Wiley
Date: 07-10-2010
Abstract: Herein trimethylsilane (TMS) is demonstrated to be an efficient binding group suitable for construction of metal-molecule-metal (M-mol-M') junctions, in which one of the metal contacts is an atomically flat gold surface and the other a scanning tunnelling microscopy (STM) tip. The molecular component of the M-mol-M' devices is an oligomeric phenylene ethynylene (OPE) derivative Me(3)Si C≡C{C(6)H(4)C≡C}(2)C(6)H(4)NH(2), featuring both Me(3)SiC≡C and NH(2) metal contacting groups. This compound can be assembled into Langmuir-Blodgett (LB) films on Au--substrates by surface binding through the amine groups. Alternatively, low coverage (sub-monolayer) films are formed by adsorption from solution. In the case of condensed monolayers top electrical contacts are formed to STM tips through the TMS end group. In low coverage films, single molecular bridges can be formed between the gold surface and a gold STM tip. The similarity in the I-V response of a one-layer LB film and the single molecule conductance experiments reveals several points of critical importance to the design of molecular components for use in the construction of M-mol-M' junctions. Firstly, the presence of neighbouring π systems does not have a significant effect on the conductance of the M-mol-M' junction. Secondly, in the STM configuration, intermolecular electron hopping does not significantly enhance the junction transport characteristics. Thirdly, the symmetric behaviour of the I-V curves obtained, despite the different metal-molecule contacts, indicates that the molecule is simply an hiphilic electron-donating wire and not a molecular diode with strong rectifying characteristics. Finally, the conductance values obtained from the amine/TMS-contacted OPE described here are of the same order of magnitude as thiol anchored OPEs, making them attractive alternatives to the more conventionally used thiol-contacting chemistry for OPE molecular wires.
Metal Cluster Terminated “Molecular Wires”
Publisher: Springer Science and Business Media LLC
Date: 04-01-2006
Expeditious synthesis of Re3(μ-H)3(CO)11(NCMe)
Publisher: Elsevier BV
Date: 07-1996
Redox‐Addressable Single‐Molecule Junctions Incorporating a Persistent Organic Radical**
Publisher: Wiley
Date: 05-04-2022
Abstract: Integrating radical (open‐shell) species into non‐cryogenic nanodevices is key to unlocking the potential of molecular electronics. While many efforts have been devoted to this issue, in the absence of a chemical/electrochemical potential the open‐shell character is generally lost in contact with the metallic electrodes. Herein, single‐molecule devices incorporating a 6‐oxo‐verdazyl persistent radical have been fabricated using break‐junction techniques. The open‐shell character is retained at room temperature, and electrochemical gating permits in situ reduction to a closed‐shell anionic state in a single‐molecule transistor configuration. Furthermore, electronically driven rectification arises from bias‐dependent alignment of the open‐shell resonances. The integration of radical character, transistor‐like switching, and rectification in a single molecular component paves the way to further studies of the electronic, magnetic, and thermoelectric properties of open‐shell species.
Ir(III)-Based Phosphors with Bipyrazolate Ancillaries; Rational Design, Photophysics, and Applications in Organic Light-Emitting Diodes
Publisher: American Chemical Society (ACS)
Date: 03-11-2015
DOI: 10.1021/ACS.INORGCHEM.5B01835
Abstract: A series of three charge-neutral Ir(III) complexes bearing both neutral chelating ligands 4,4'-di-t-butyl-2,2'-bipyridine (dtbbpy) and monoanionic cyclometalated ligands derived from 2-phenylpyridine (ppyH), together with either two monoanionic ligands (i.e., chloride and monodentate pyrazolate) or a single dianionic chelate derived from 5,5'-di(trifluoromethyl)-3,3'-bipyrazole (bipzH2) or 5,5'-(1-methylethylidene)-bis-(3-trifluoromethyl-1H-pyrazole) (mepzH2), was successfully synthesized. These complexes are derived from a common, structurally characterized, Ir(III) intermediate complex [Ir(dtbbpy) (ppy)Cl2] (1), from treatment of IrCl3·3H2O with equal amount of the diimine (N^N) and precursor of the cyclometalated (C^N) ligands in a form of one-pot reaction. Treatment of 1 with various functional pyrazoles afforded [Ir(dtbbpy) (ppy) (pz)Cl] (2), [Ir(dtbbpy) (ppy) (bipz)] (3), and [Ir(dtbbpy) (ppy) (mepz)] (4), which display intense room-temperature emission with λmax spanning the region between 532 and 593 nm in both fluid and solid states. The Ir(III) complexes, 3 and 4, showcase rare ex les of three distinctive chelates (i.e., neutral, anionic, and dianionic) assembled around the central Ir(III) cation. Hybrid density functional theory (DFT B3LYP) electronic structure calculations on 1-4 reveal the lowest unoccupied molecular orbital to be π*(bpy) in character for all complexes and highest occupied molecular orbital (HOMO) offering d(Ir)-π(phenyl) character for 1, 2, and 4 and π(bipz) character for 3. The different HOMO composition of 3 and 4 is also predicted by calculations using pure DFT (BLYP) and wave function (MP2) methods. On the basis of time-dependent DFT calculations, the emissive processes are dominated by the phenyl group-to-bipyridine, ligand(ppy)-to-ligand(bpy) charge transfer admixed with metal-to-ligand transition for all Ir(III) complexes. Organic light emitting diodes were successfully fabricated. A double emitting layer design was adopted in the device architecture using Ir(III) metal complexes 3 and 4, attaining peak external quantum efficiencies, luminance efficiencies, and power efficiencies of 18.1% (59.0 cd/A and 38.6 lm/W) and 16.6% (53.3 cd/A and 33.5 lm/W), respectively.
The syntheses, structures and spectroelectrochemical properties of 6-oxo-verdazyl derivatives bearing surface anchoring groups
Publisher: American Chemical Society (ACS)
Date: 16-11-2021
DOI: 10.26434/CHEMRXIV-2021-TQJWG
Abstract: A series of 6-oxo verdazyl radicals functionalised at the 1- and 5-positions by methyl, thiomethyl and iodo groups were synthesised using conventional strategies. Facile Sonogashira cross-coupling reactions of terminal alkynes with the diiodo analogue were used for synthetic elaboration of the verdazyl core structure with π-conjugated ethynyl groups. The radicals were characterised by EPR spectroscopy, single-crystal X-ray diffraction, cyclic voltammetry and optical spectroscopy. The chemically and electrochemically reversible oxidation and reduction of these radicals within a convenient redox window permitted further studies on the closed-shell cationic and anionic forms using spectroelectrochemical methods, supported by (TD-)DFT calculations.
Two tetracobalt cluster complexes: Preparation and molecular structures of Co4(μ-dppm)2(μ-CO)3(CO)5 and Co4(μ-CO)3(CO)6(η-C6 H6)
Publisher: CSIRO Publishing
Date: 2001
DOI: 10.1071/CH01077
Further Evidence for ‘Extended’ Cumulene Complexes: Derivatives from Reactions with Halide Anions and Water
Publisher: Wiley
Date: 28-04-2020
High surface coverage of a self-assembled monolayer by in situ synthesis of palladium nanodeposits.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7NR03365F
Abstract: Nascent metal|monolayer|metal devices have been fabricated by depositing palladium, produced through a CO-confined growth method, onto a self-assembled monolayer of an amine-terminated oligo(phenylene ethynylene) derivative on a gold bottom electrode. The high surface area coverage (85%) of the organic monolayer by densely packed palladium particles was confirmed by X-ray photoemission spectroscopy (XPS) and atomic force microscopy (AFM). The electrical properties of these nascent Au|monolayer|Pd assemblies were determined from the I-V curves recorded with a conductive-AFM using the Peak Force Tunneling AFM (PF-TUNA™) mode. The I-V curves together with the electrochemical experiments performed rule out the formation of short-circuits due to palladium penetration through the monolayer, suggesting that the palladium deposition strategy is an effective method for the fabrication of molecular junctions without damaging the organic layer.
Optimised Syntheses of the Half-Sandwich Complexes FeCl(dppe)Cp*, FeCl(dppe)Cp, RuCl(dppe)Cp*, and RuCl(dppe)Cp
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH16322
Abstract: Thanks to their synthetic versatility, the half-sandwich metal chlorides MCl(dppe)(η5-C5R5) [M = Fe, Ru dppe = 1,2-bis(diphenylphosphino)ethane, R = H (cyclopentadiene, Cp), CH3 (pentamethylcyclopentadiene, Cp*)] are staple starting materials in many organometallic laboratories. Here we present an overview of the synthetic methods currently available for FeCl(dppe)Cp*, FeCl(dppe)Cp, RuCl(dppe)Cp*, and RuCl(dppe)Cp, and describe in detail updated and optimised multigram syntheses of all four compounds.
Near infrared-emitting tris-bidentate Os(ii ) phosphors: control of excited state characteristics and fabrication of OLEDs
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5TC00204D
Abstract: Os( ii ) complexes bearing chromophoric 1,10-phenanthroline, diphosphine and bipyrazolate ancillaries display efficient NIR emission ranging from 717 nm to 779 nm in the solid state at RT.
Transition metal alkynyl complexes by transmetallation from Au(CCAr)(PPh3) (Ar = C6H5or C6H4Me-4)
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B809960J
Abstract: Facile acetylide transfer reactions take place between gold(I) complexes Au(C[triple bond]CAr)(PPh3) (Ar = C6H5 or C6H4Me-4) and a variety of representative inorganic and organometallic complexes MXL, (M = metal, X = halide, L, = supporting ligands) featuring metals from groups 8-11, to afford the corresponding metal-alkynyl complexes M(C[triple bond]CR)Ln in modest to good yield. Reaction products have been characterised by spectroscopic methods, and molecular structure determinations are reported for Fe(C[triple bond]CC6H4Me-4)(dppe)Cp, Ru(C[triple bond]CC6H4Me-4)(dppe)Cp*, Ru(C=CCsF,)(l2-O2)(PPh3)Cp*, Ir(C-CC6H4Me-4)(eta2-O2)(CO)(PPh3), Ni(C[triple bond]CC6H4Me-4)(PPh3)Cp and trans-Pt(C[triple bond]CAr)2L2 (Ar = C6H5, L = PPh3 Ar = C6H4Me-4, L = PPh3, PMe3).
Electrochemical and spectroelectrochemical studies of C-benzodiazaborolyl-ortho-carboranes
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2DT32378H
Abstract: Fifteen C-diazaborolyl-ortho-carboranes, 1-R'-2-R''-1,2-C(2)B(10)H(10), where R' represents the groups 2-(1,3-Et(2)-1,3,2-N(2)BC(6)H(4))-, 2-(1,3-Ph(2)-1,3,2-N(2)BC(6)H(4))-, 2-(1,3-Ph(2)-5,6-Me(2)-1,3,2-N(2)BC(6)H(2))-, 2-(1,3-(i)Pr(2)-1,3,2-N(2)BC(6)H(4))-, and 2-(1,3,2-N(2)BC(6)H(6))- and where R'' is H, Me, Ph, (t)Bu or SiMe(3), were synthesized. Cyclic voltammetry studies of the compounds showed irreversible oxidation waves which are caused by the oxidation of the heterocycle. Those C-diazaborolyl-ortho-carboranes with Ph, tBu and SiMe(3) substituents at the adjacent C-atom of the cage displayed two one-electron reduction waves reflecting the formation of stable radical monoanions with unusual (2n + 3) skeletal electron counts. The geometries of these anions were determined by combinations of infrared, UV-visible spectroelectrochemical and computational studies. Additionally the structures of seven new C-diazaborolyl-ortho-carboranes and one new 2-bromo-1,3,2-benzodiazaborole were determined by X-ray crystallography and compared with previously obtained structures.
Redox‐Addressable Single‐Molecule Junctions Incorporating a Persistent Organic Radical**
Publisher: Wiley
Date: 05-04-2022
Abstract: Integrating radical (open‐shell) species into non‐cryogenic nanodevices is key to unlocking the potential of molecular electronics. While many efforts have been devoted to this issue, in the absence of a chemical/electrochemical potential the open‐shell character is generally lost in contact with the metallic electrodes. Herein, single‐molecule devices incorporating a 6‐oxo‐verdazyl persistent radical have been fabricated using break‐junction techniques. The open‐shell character is retained at room temperature, and electrochemical gating permits in situ reduction to a closed‐shell anionic state in a single‐molecule transistor configuration. Furthermore, electronically driven rectification arises from bias‐dependent alignment of the open‐shell resonances. The integration of radical character, transistor‐like switching, and rectification in a single molecular component paves the way to further studies of the electronic, magnetic, and thermoelectric properties of open‐shell species.
Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B808798A
Abstract: Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) and RuCl(dppe)Cp' [Cp' = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C[triple bond, length as m-dash]CC(6)F(5))(dppe)Cp' [Cp' = Cp () Cp* ()], which are related to the known compound Ru(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3))(2)Cp (). Treatment of Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) with Pt(2)(mu-dppm)(2)Cl(2) in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt(2)(mu-dppm)(2)(C[triple bond, length as m-dash]CC(6)F(5))(2) (). The Pd(0)/Cu(i)-catalysed reactions between Au(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3)) and Mo( identical withCBr)(CO)(2)Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co(3)(mu(3)-CBr)(mu-dppm)(CO)(7) or IC[triple bond, length as m-dash]CFc [Fc = (eta(5)-C(5)H(4))FeCp] afford Mo( identical withCC[triple bond, length as m-dash]CC(6)F(5))(CO)(2)Tp* (), Co(3)(mu(3)-CC[triple bond, length as m-dash]CC(6)F(5))(mu-dppm)(CO)(7) () and FcC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC(6)F(5) (), respectively. The diruthenium complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)F(4) [(PP)Cp' = (PPh(3))(2)Cp () (dppe)Cp () (dppe)Cp* ()] are prepared from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)F(4) in a manner similar to that described for the monoruthenium complexes -. The non-fluorinated complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)H(4) [(PP)Cp' = (PPh(3))(2)Cp () (dppe)Cp () (dppe)Cp* ()], prepared for comparison, are obtained from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)H(4). Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes - and -, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes , , , and .
Rhenium complexes from alkynes. X-Ray crystal structures of Re2(μ-2η1,-C4Ph4) (CO)7 and Re{C,O-CH C[Re(CO)4(NMe3)]C(OMe)O}(CO)4
Publisher: Elsevier BV
Date: 1994
The preparation and characterisation of ruthenium cyanovinylidene complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B714274A
Abstract: Reactions of half-sandwich ruthenium metal acetylide complexes with 1-cyano-4-dimethylaminopyridinium salts afford complexes containing mono- or di-cyanovinylidene ligands the procedure can be adapted to permit the simple synthesis of a cyanoacetylide complex, via the in situ deprotonation of a primary cyanovinylidene complex.
A one-pot synthesis of oligo(arylene–ethynylene)-molecular wires and their use in the further verification of molecular circuit laws
Publisher: CSIRO Publishing
Date: 23-02-2022
DOI: 10.1071/CH21235
Abstract: A convenient two-step, one-pot synthesis of oligo(arylene–ethynylene) (OAE) type molecular wires in yields of up to 70% via in situ desilylation of protected bis(alkynes) Me3SiC≡CArC≡CSiMe3 (Ar = 2,5-thienyl, 1,4-naphthylene, 9,10-anthrylene) and subsequent Sonogashira cross-coupling with S-(4-iodophenyl) ethanethiolate, 4-iodothioanisole, or 5-bromo-3,3-dimethyl-2,3-dihydrobenzo[b]thiophene is described. The in situ desilylation avoids the manipulation of the sensitive terminal dialkynes (HC≡CArC≡CH), whilst the general approach presented has some advantages over alternative synthetic strategies based on coupling of aryl dihalides (XArX) by avoiding the multi-step preparation and purification of the terminal alkynes S-(4-ethynylphenyl) ethanethiolate, 4-ethynylthioanisole and 5-ethynyl 3,3-dimethyl-2,3-dihydrobenzo[b]thiophene. The molecular conductance of the resulting thiolate or thioether functionalised OAE molecular wires has been determined using scanning tunneling microscope break junction (STM-BJ) methods. The trends in molecular conductance do not track simply with the degree of aromaticity of the molecular core despite the rather similar molecular lengths. Rather, the STM-BJ data are better correlated with the nature of the anchor group, highlighting the important role of electrode–molecule coupling on electron transport in a molecular junction. The experimental conductance data are in good agreement with recently described quantum circuit rules, further highlighting the potential for these relationships to be used as predictive tools in molecular electronics research.
The syntheses, structures and redox properties of phosphine-gold(I) and triruthenium-carbonyl cluster derivatives of tolans
Publisher: Elsevier BV
Date: 05-2008
Orbital Symmetry Control of Electronic Coupling in a Symmetrical, All-Carbon-Bridged “Mixed Valence” Compound: Synthesis, Spectroscopy, and Electronic Structure of [{Mo(dppe)(η-C7H7
Publisher:
American Chemical Society (ACS)
Date:
12-12-2011
DOI:
10.1021/OM200712M
Clusters as ligands: Synthesis, structure and coordination chemistry of ruthenium clusters derived from 4- and 5-ethynyl-2,2′-bipyridine
Publisher: Elsevier BV
Date: 06-2016
All‐Carbon Electrode Molecular Electronic Devices Based on Langmuir–Blodgett Monolayers
Publisher: Wiley
Date: 16-12-2016
Abstract: Nascent molecular electronic devices, based on monolayer Langmuir-Blodgett films sandwiched between two carbonaceous electrodes, have been prepared. Tightly packed monolayers of 4-((4-((4-ethynylphenyl)ethynyl)phenyl)ethynyl)benzoic acid are deposited onto a highly oriented pyrolytic graphite electrode. An amorphous carbon top contact electrode is formed on top of the monolayer from a naphthalene precursor using the focused electron beam induced deposition technique. This allows the deposition of a carbon top-contact electrode with well-defined shape, thickness, and precise positioning on the film with nm resolution. These results represent a substantial step toward the realization of integrated molecular electronic devices based on monolayers and carbon electrodes.
Acetylide generation and coupling on electron-rich Ru3 clusters
Publisher: Royal Society of Chemistry (RSC)
Date: 06-03-2002
DOI: 10.1039/B108626J
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