ORCID Profile
0000-0003-1603-7994
Current Organisation
Monash University
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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.
Transition Metal Chemistry | Inorganic Chemistry | Macromolecular and Materials Chemistry | Solid State Chemistry | Nanochemistry and Supramolecular Chemistry | Bioinorganic chemistry | Biologically active molecules | Characterisation of Biological Macromolecules | Physical Chemistry of Materials | Synthesis of Materials | Transition Metal Chemistry | F-Block Chemistry | Non-Metal Chemistry | Physical Chemistry (Incl. Structural) | F-Block Chemistry | Structural Chemistry and Spectroscopy | Inorganic chemistry | Electronic and Magnetic Properties of Condensed Matter; Superconductivity
Expanding Knowledge in the Chemical Sciences | Chemical sciences | Expanding Knowledge in Technology | Industrial Chemicals and Related Products not elsewhere classified | Expanding Knowledge in the Physical Sciences | Expanding Knowledge in the Biological Sciences |
Publisher: American Chemical Society (ACS)
Date: 13-07-2009
DOI: 10.1021/IC9010967
Abstract: Heteroligand molecular "stirrups" form by the self-assembly of flexible ditopic ligands in combination with 4,4'-bipyridine and [(dppp)Pd)](2+). Crystallographic analysis shows that the ligands, bis[3-(4-pyridyl)pyrazolyl]-m-xylene (mXy(4py3pz)) and bis[4-(4-pyridyl)pyrazolyl]-p-xylene (pXy(4py4pz)) form complexes of the type [{(dppp)Pd}(2)(4,4'-bipy)(L)].4OTf (1.4OTf and 2.4OTf, respectively) in the solid state, with remarkably similar structures considering the differences in substitution patterns between the two ligands. The self-assembly of both 1(4+) and 2(4+) is assisted by face-to-face pi interactions on the exterior of the macrocycle between the phenyl rings of the dppp ligands and the pyridyl groups of the ditopic ligands.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CE01000H
Abstract: Four isomeric pyridyl/carboxylate ligands demonstrate the appliability of low-symmetry ligands to the formation of chiral materials.
Publisher: Wiley
Date: 24-07-2019
Abstract: The metallosupramolecular chemistry of two enantiopure dicarboxylate ligands has been explored for their potential to form discrete or polymeric interlocked motifs. Consequently, both discrete and polymeric supramolecular complexes have been synthesised, yielding M
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5DT02323H
Abstract: Studies into a series of coordination polymers from a new diamine polycarboxylate ligand reveal an interplay between flexibility and material properties.
Publisher: Elsevier BV
Date: 2010
Publisher: American Chemical Society (ACS)
Date: 12-02-2014
DOI: 10.1021/IC402672M
Abstract: Three complexes of the form [Ln(III)3(OQ)9] (Ln = Gd, Tb, Dy OQ = 8-quinolinolate) have been synthesized and their magnetic properties studied. The trinuclear complexes adopt V-shaped geometries with three bridging 8-quinolinolate oxygen atoms between the central and peripheral eight-coordinate metal atoms. The magnetic properties of these three complexes differ greatly. Variable-temperature direct-current (dc) magnetic susceptibility measurements reveal that the gadolinium and terbium complexes display weak antiferromagnetic nearest-neighbor magnetic exchange interactions. This was quantified in the isotropic gadolinium case with an exchangecoupling parameter of J = -0.068(2) cm(-1). The dysprosium compound displays weak ferromagnetic exchange. Variable-frequency and -temperature alternating-current magnetic susceptibility measurements on the anisotropic cases reveal that the dysprosium complex displays single-molecule-magnet behavior, in zero dc field, with two distinct relaxation modes of differing time scales within the same molecule. Analysis of the data revealed anisotropy barriers of Ueff = 92 and 48 K for the two processes. The terbium complex, on the other hand, displays no such behavior in zero dc field, but upon application of a static dc field, slow magnetic relaxation can be observed. Ab initio and electrostatic calculations were used in an attempt to explain the origin of the experimentally observed slow relaxation of the magnetization for the dysprosium complex.
Publisher: International Union of Crystallography (IUCr)
Date: 26-07-2006
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2NJ00997H
Abstract: The synthesis of a series of novel organotellurium species and diorganoselenones is reported.
Publisher: Elsevier BV
Date: 06-2007
Publisher: American Chemical Society (ACS)
Date: 21-06-2016
DOI: 10.1021/ACS.INORGCHEM.6B00933
Abstract: A long and highly flexible internally functionalized dipyridyl ligand α,α'-p-xylylenebis(1-(4-pyridylmethylene)-piper-4-azine), L, has been employed in the synthesis of a series of coordination polymer materials with Co(II), Cd(II), and Ag(I) ions. In poly-[Cd(L)(TPA)] 1 and poly-[Co(L)(IPA)], 2, (TPA = terephthalate, IPA = isophthalate) the ligand adopts a similar linear conformation to that seen in the structure of the unbound molecule and provides a long (2.6 nm) metal-metal bridging distance. Due to the mismatch of edge lengths with that provided by the carboxylate coligands, geometric distortions from the regular dia and (4,4) network geometries for 1 and 2, respectively, are observed. In poly-[Ag2(CF3SO3)2(L)], 3, the ligand coordinates through both pyridine groups and two of the four piperazine nitrogen donors, forming a high-connectivity 2-dimensional network. The compound poly-[Ag2(L)](BF4)2·2MeCN, 4, a porous 3-dimensional cds network, undergoes a fascinating and rapid single-crystal-to-single-crystal rearrangement on exchange of the acetonitrile guests for water in ambient air, forming a nonporous hydrated network poly-[Ag2(L)](BF4)2·2H2O, 5, in which the well-ordered guest water molecules mediate the rearrangement of the tetrafluoroborate anions and the framework itself through hydrogen bonding. The dynamics of the system are examined in greater detail through the preparation of a kinetic product, the dioxane-solvated species poly-[Ag2(L)](BF4)2·2C4H8O2, 6, which undergoes a slow conversion to 5 over the course of approximately 16 h, a transition which can be monitored in real time. The reverse transformation can also be observed on immersing the hydrate 5 in dioxane. The structural features and physical properties of each of the materials can be rationalized based on the flexible and multifunctional nature of the ligand molecule, as well as the coordination behavior of the chosen metal ions.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT31144E
Abstract: The isostructural heterometallic complexes [Ln(III)(2)Mn(III)(2)O(2)(ccnm)(6)(dcnm)(2)(H(2)O)(2)] (Ln = Eu (1Eu), Gd (1Gd), Tb (1Tb), Er (1Er) ccnm = carbamoylcyanonitrosomethanide dcnm = dicyanonitrosomethanide) have been synthesised and structurally characterised. The in situ transition metal promoted nucleophilic addition of water to dcnm, forming the derivative ligand ccnm, plays an essential role in cluster formation. The central [Ln(III)(2)Mn(III)(2)(O)(2)] moiety has a "butterfly" topology. The coordinated aqua ligands and the NH(2) group of the ccnm ligands facilitate the formation of a range of hydrogen bonds with the lattice solvent and neighbouring clusters. Magnetic measurements generally reveal weak intracluster antiferromagnetic coupling, except for the large J(MnMn) value in 1Gd. There is some evidence for single molecule magnetic (SMM) behaviour in 1Er. Comparisons of the magnetic properties are made with other recently reported butterfly-type {Ln(III)(x)M(III)(4-x) (d-block)} clusters, x = 1, 2 M = Mn, Fe.
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B716191C
Publisher: Wiley
Date: 16-07-2021
Abstract: The controlled oxidation reaction of L‐selenocystine under neutral pH conditions affords selenocysteine seleninic acid (3‐selenino‐L‐alanine) which is characterized also by means of single‐crystal X‐ray diffraction. This technique shows that selenium forms three chalcogen bonds (ChBs), one of them being outstandingly short. A survey of seleninic acid derivatives in the Cambridge Structural Database (CSD) confirms that the C−Se(=O)O− functionality tends to act as a ChB donor robust enough to systematically influence the interactional landscape in the solid. Quantum Theory of Atom in Molecules (QTAIM) analysis proves the attractive nature of the short contacts observed in crystals containing the seleninic functionality and calculation of surface molecular electrostatic potential (MEP) reveals that remarkably positive σ‐holes can frequently be found opposite to the covalent bonds at selenium. Both CSD searches and QTAIM and MEP approaches show that also the sulfinic acid moiety can function as a ChB donor, albeit less frequently than the seleninic acid one. These findings may contribute to a better understanding, at the atomic level, of the mechanism of action of the enzymes that control oxidative stress and ROS deactivation and that contain selenocysteine seleninic acid and cysteine sulfinic acid in the active site.
Publisher: Proceedings of the National Academy of Sciences
Date: 09-04-2002
Abstract: A series of podands based on two or three hydrogen bonding “arms” situated in mutually ortho , meta , or para relationships about an aryl core have been prepared, and their affinities for simple inorganic anions were measured. Of the two-arm hosts the meta compound and to a lesser extent the ortho host exhibit a cooperative anion binding effect. The two arms function essentially independently in the para derivative. The mutually meta three-arm host shows dramatically enhanced cooperative binding. Conformational changes within the meta two-arm host result in significantly enhanced electrochemical anion sensing compared with the more conformationally rigid three-arm host.
Publisher: Wiley
Date: 28-04-2009
Abstract: The metal-promoted nucleophilic addition of diaminoalkanes to dicyanonitrosomethanide, C(CN)2(NO)- (dcnm), and subsequent cyclization has been utilized in the synthesis of novel anionic species. The addition and cyclization of 1,2-diaminoethane (en) to both nitrile groups of dcnm forms the anion diimidazolinylnitrosomethanide (dinm), isolated in the dinuclear complex [{Cu(dinm)(en)}2en][ClO4]2 (1). The same reaction solution yields [Cu(cinm)(ainm)] (cinm=cyanoimidazolinylnitrosomethanide, ainm=(((2-aminoethyl)amino)iminomethyl)imidazolinylnitrosomethanide) (2), which contains intermediates of the dinm species, supporting a stepwise mechanism of addition of the diamine followed by cyclization. 1,3-Diaminopropane (pn) added and cyclized on only one nitrile group to form a 1,4,5,6-tetrahydropyrimidine ring. This resulted in the formation of the cyanonitroso-1,4,5,6-tetrahydropyrimidinylmethanide ligand (cnpm) in complexes with the general formula [M(cnpm)2(pn)] (M=Cu (3a), Ni (3b), Zn (3c)). These reactions are contrasted to the addition of ethanolamine in the pyridine (py) complex [Ni(chnm)2(py)2].(py) (4) (chnm=cyano((2-hydroxyethyl)amino)iminomethylnitrosomethanide) with no cyclization, demonstrating the higher reactivity of amines compared with alcohols. The formation of the complexes [M(cmnm)2(mame)] (M=Co (5a), Ni (5b), cmnm=cyano(imino(methoxy)methyl)nitrosomethanide, mame=1-dimethylamino-2-methylaminoethane) indicate mame may be too sterically hindered to add to dcnm under similar reaction conditions.
Publisher: CSIRO Publishing
Date: 2019
DOI: 10.1071/CH19194
Abstract: The solvothermal reaction of 2-nitro-[1,1′‐biphenyl]‐4,4′‐dicarboxylic acid (H2bpdcNO2) with Zn(NO3)2·6H2O in DMF solvent does not give a functionalised variant of IRMOF-9. Single-crystal X-ray diffraction analysis shows the major initial product of this reaction, WUF-21 (WUF=Wollongong University Framework), is a porous interpenetrated diamondoid metal–organic framework (MOF) with a secondary building unit that ‘doubly straps’ eight bridging bpdcNO2 ligands in a distorted tetrahedral shape around an unusual pentazinc core. A second porous MOF phase (WUF-23) containing a large and novel dodecazinc secondary building unit forms in the same reaction and eventually predominates in solutions containing formate anion, which arises from the hydrolysis of DMF. Doping the starting ligand with [1,1′‐biphenyl]‐4,4′‐dicarboxylic acid (H2bpdc) provides a facile way to grow nitro-functionalised IRMOF-9, hereafter denoted as WUF-22, where the dopant is carried through into the product. Activated WUF-22 is a microporous solid with an apparent Brunauer–Emmett–Teller (BET) surface area of 2497m2g−1, which matches well with geometric surface area calculations. The CO2 adsorption properties of WUF-22 are reported.
Publisher: American Chemical Society (ACS)
Date: 24-02-2023
DOI: 10.26434/CHEMRXIV-2023-95ZL8
Abstract: Understanding the intricacies of self-assembly and ligand exchange has wide-ranging applicability in current inorganic chemistry and in the future design and assembly of complex, functional materials incorporating metal-ligand motifs. Ligand exchange between two paddlewheel-based M4L4 cages results in the formation of a near-statistical mixture of homo- and hetero-leptic species. Steric bulk allows tuning of the lability of the ligands in the coordination cage complexes with bulkier ligands forming cages having half-lives ca. three times that of the least hindered species. Solvent plays an important role in the lability of the ligands of the coordination cages larger solvent molecules coordinated to the exterior of the metal nodes provide a stabilizing effect, slowing the rate of ligand exchange. In some instance the final equilibrium position is slightly perturbed by the combination of steric bulk from the two ligands, suggesting that the self-assembly process are not trivial.
Publisher: American Chemical Society (ACS)
Date: 08-2008
DOI: 10.1021/CG800247F
Publisher: Royal Society of Chemistry (RSC)
Date: 2005
DOI: 10.1039/B415818K
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B702473H
Abstract: The complexes [Et(4)N](3)[Ln(eta(2)-dcnm)(6)] (Ln = La, Ce, Nd, Gd, dcnm = dicyanonitrosomethanide) have discrete N, O 12-coordination owing to symmetrical chelation of the nitroso donor groups.
Publisher: Wiley
Date: 31-10-2014
DOI: 10.1111/COBI.12416
Abstract: Systematic conservation planning optimizes trade-offs between bio ersity conservation and human activities by accounting for socioeconomic costs while aiming to achieve prescribed conservation objectives. However, the most cost-efficient conservation plan can be very dissimilar to any other plan achieving the set of conservation objectives. This is problematic under conditions of implementation uncertainty (e.g., if all or part of the plan becomes unattainable). We determined through simulations of parallel implementation of conservation plans and habitat loss the conditions under which optimal plans have limited chances of implementation and where implementation attempts would fail to meet objectives. We then devised a new, flexible method for identifying conservation priorities and scheduling conservation actions. This method entails generating a number of alternative plans, calculating the similarity in site composition among all plans, and selecting the plan with the highest density of neighboring plans in similarity space. We compared our method with the classic method that maximizes cost efficiency with synthetic and real data sets. When implementation was uncertain--a common reality--our method provided higher likelihood of achieving conservation targets. We found that χ, a measure of the shortfall in objectives achieved by a conservation plan if the plan could not be implemented entirely, was the main factor determining the relative performance of a flexibility enhanced approach to conservation prioritization. Our findings should help planning authorities prioritize conservation efforts in the face of uncertainty about future condition and availability of sites.
Publisher: American Chemical Society (ACS)
Date: 18-11-2010
DOI: 10.1021/JP108550Z
Abstract: In this work the nucleophilic addition of water and methanol to the dicyanonitrosomethanide anion (dcnm, [C(CN)(2)(NO)](-)) in the absence of the usual transition metal promoters was investigated. Experimentally it was shown that a quantitative conversion of the dcnm anion to carbamoylcyanonitrosomethanide (ccnm, [C(CN)(CONH(2))(NO)](-)) by the addition of 1 equiv of water to a nitrile group is complete in 48 h at 100 °C, or in 1.5 h at 150 °C when the reaction is conducted in a microwave reactor. Attempts to add a second equivalent of water to the anion failed with thermal degradation of the anion occurring at 200 °C. Ab initio calculations show that the reaction proceeds via three distinct transition states: (1) the transfer of a proton from a water molecule to the nitrile group, (2) the subsequent attack of the generated hydroxide anion on the carbon atom of the nitrile group, and (3) a rapid proton transfer to form a carbamoyl group. The attacking water molecule is shown to be a stronger proton donor when modeled as part of a hydrogen-bonded three water molecule chain, leading to a significant reduction in the reaction barrier. Only the anti-ccnm anion is formed in the reaction. There is a high-energy barrier to the formation of the syn isomer by the rotation of the nitroso group. While the syn isomer of ccnm is shown to be the more thermodynamically stable conformation, examination of the HOMO-1 molecular orbital that arises during the second transition state of the reaction indicates the addition of the hydroxide anion to the carbon atom is forbidden due to orbital symmetry, with a similar effect responsible for the failure of a second equivalent of water to add to the ccnm anion. Under analogous reaction conditions the addition of 1 equiv of methanol to dcnm to form cyano(imino(methoxy)methyl)nitrosomethanide (cmnm, [C(CN)(C(OMe)NH)(NO)](-)) failed, although ab initio calculations initially indicated the reaction should proceed more readily than the addition of water. When the energy required to break the hydrogen-bonded cyclic hexamers in methanol is taken into consideration, the energy barrier to the first transition step is greatly increased. The addition of a second equivalent of methanol to cmnm is unlikely to occur even in the presence of a transition metal as the resultant anion would be marginally thermodynamically unstable.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CE00744F
Abstract: Small changes in the steric bulk in bis(amino acid) naphthalene diimides are shown to have a very significant impact on the structural motifs that are observed in coordination polymers containing the dicarboxylate ligands.
Publisher: American Chemical Society (ACS)
Date: 28-10-2014
DOI: 10.1021/IC5016115
Abstract: New insights into the synthesis of high-nuclearity polycarbonatolanthanoid complexes have been obtained from a detailed investigation of the preparative methods that initially yielded the so-called "lanthaballs" [Ln(13)(ccnm)(6)(CO(3))(14)(H(2)O)(6)(phen)(18)] Cl(3)(CO(3))·25H(2)O [α-1Ln Ln = La, Ce, Pr phen = 1,10-phenanthroline ccnm = carbamoylcyanonitrosomethanide]. From this investigation, we have isolated a new pseudopolymorph of the cerium analogue of the lanthaball, [Ce(13)(ccnm)(6)(CO(3))(14)(H(2)O)(6)(phen)(18)]·C(l3)·CO(3) (β-1Ce). This new pseudopolymorph arose from a preparation in which fixation of atmospheric carbon dioxide generated the carbonate, and the ccnm ligand was formed in situ by the nucleophilic addition of water to dicyanonitrosomethanide. From a reaction of cerium(III) nitrate, instead of the previously used chloride salt, with (Et4N)(ccnm), phen, and NaHCO(3) in aqueous methanol, the new complex Na[Ce(13)(ccnm)(6)(CO(3))(14)(H(2)O)(6)(phen)(18)](NO(3))(6)·20H(2)O (2Ce) crystallized. A variant of this reaction in which sodium carbonate was initially added to Ce(NO(3))(3), followed by phen and (Et(4)N)(ccnm), also gave 2Ce. However, an analogous preparation with (Me4N)(ccnm) gave a mixture of crystals of 2Ce and the coordination polymer [CeNa(ccnm)4(phen)3]·MeOH (3), which were manually separated. The use of cerium(III) acetate in place of cerium nitrate in the initial preparation did not give a high-nuclearity complex but a new coordination polymer, [Ce(ccnm)(OAc)(2)(phen)] (4). The first lanthaball to incorporate neodymium, namely, [Nd(13)(ccnm)(4)(CO(3))14(NO(3))(4)(H(2)O)(7)(phen)(15)](NO(3))(3)·10H(2)O (5Nd), was isolated from a preparation similar to that of the second method used for 2Ce, and its magnetic properties showed an antiferromagnetic interaction. The identity of all products was established by X-ray crystallography.
Publisher: Wiley
Date: 22-08-2006
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1CC11909E
Abstract: The chemistry of the anions dicyanamide and tricyanomethanide (dca and tcm, respectively) has produced a plethora of discoveries over the past few decades, particularly in relation to transition-metal coordination polymers with magnetic coupling. Over recent years there have been an increasing number of reports of heterofunctionalised cyano-containing anions, typically derivatives of dicyanomethanide. Our own group has been particularly concerned with the amide- and nitroso-functionalised anions carbamoyldicyanomethanide (cdm) and dicyanonitrosomethanide (dcnm), respectively. This feature article examines the fascinating ersity of materials and complexes that can be obtained using small cyano anions, ranging from coordination polymers to heterometallic clusters and hydrogen bonding networks. In particular, we focus on results from our own laboratories in the past few years. The magnetic properties of these materials are briefly discussed.
Publisher: Wiley
Date: 22-05-2018
Abstract: An understanding of the atomic-scale interactions between gas sorbent materials and their molecular guests is essential for the identification of the origins of desirable function and the rational optimization of performance. However, characterizations performed on equilibrated sorbent-guest systems may not accurately represent their behavior under dynamic operating conditions. The emergence of fast (minute-scale) neutron powder diffraction coupled with direct, real-time quantification of gas uptake opens up new possibilities for obtaining knowledge about concentration-dependent effects of guest loading upon function-critical features of sorbent materials, including atomic structure, diffusion pathways, and thermal expansion of the sorbent framework. This article presents a detailed investigation of the ultramicroporous metal-organic framework [Cu
Publisher: Elsevier BV
Date: 2007
Publisher: Elsevier BV
Date: 03-2008
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9DT04013G
Abstract: The synthesis of the first ex le of a monomeric, stable organotellurinic acid is reported by utilizing the σ-hole participation of the Te atom with the N atom of the 2-(2′-pyridyl)phenyl moiety.
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B815084B
Abstract: A 2D sheet of Fe(III)(10) clusters has been synthesised in which the antiferromagnetic clusters act as 4-connecting nodes using ligands that both chelate and bridge between Fe atoms supported by diagonal hydrogen bonding.
Publisher: Elsevier BV
Date: 02-2019
Publisher: Wiley
Date: 08-03-2018
Abstract: The interdependent effects of temperature and guest uptake on the structure of the ultramicroporous metal-organic framework [Cu
Publisher: American Chemical Society (ACS)
Date: 10-12-2012
DOI: 10.1021/CM301726K
Publisher: Elsevier BV
Date: 03-2019
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B702353G
Abstract: Self-assembly and self-selection of a single linkage isomer of a mixed-metal molecular triangle with ferrocene functionality have been achieved using an ambidentate ligand, and the product was characterized by multinuclear NMR spectroscopy and X-ray single crystal structure determination.
Publisher: American Chemical Society (ACS)
Date: 16-07-2005
DOI: 10.1021/JA052081A
Abstract: Four isomorphous complexes of formula [M(L)(4)(H(2)O)(2)]SO(4).2H(2)O (M = Co, 1a Ni, 1b Cu, 1c Zn, 1d) have been isolated and characterized by single-crystal X-ray diffraction and neutron diffraction using the quasi-Laue diffractometer VIVALDI at the Institut Laue-Langevin as well as by thermogravimetric analysis. The structures contain a discrete, strongly hydrogen-bonded water tetramer which causes a significant distortion of the metal coordination sphere in each case. Partial atomic charges and hardness analysis (PACHA) calculations reveal that the shortest hydrogen bonds are not the strongest in this constrained, cyclic solid-state structure and show that the distortion at the metal center is caused by the drive to maintain the integrity of the water tetramer. The system undergoes a disorder-order transition on slow cooling that provides insight into the nature of communication between water squares.
Publisher: CSIRO Publishing
Date: 2014
DOI: 10.1071/CH14355
Abstract: A range of ethylxanthate (EtXn) salts, containing either protic or aprotic cations (guanidinium (1), methylammonium (2), dimethylammonium (3), trimethylammonium (4), tetramethylammonium (5), tetraethylammonium (6), and tetrapropylammonium (7)), have been synthesised and structurally characterised. The cations in these compounds differ in their degree of hydrogen-bonding ability, i.e. the number of donor groups, with significant structural consequences. Compounds 1–4 contain cations that are able to form N–H···S hydrogen bonds, with six, three, two, and one donor groups in 1–4 respectively. The number of donor atoms affects greatly the dimensionality of the hydrogen-bonding networks in the solid state. The structure of 1 has a 3-D hydrogen-bonding network, 2 and 3 form 2-D sheets and 1-D chains respectively, whereas the lone NH donor group in 4 has strong hydrogen bonding only within a discrete cation–anion pair. The tetraalkylammonium salts 5–7 have no strong hydrogen bonding, with only C–H···S and C–H···O interactions possible. To determine unambiguously the presence of such interactions, single-crystal Laue neutron diffraction data were obtained for compound 5, providing a fully anisotropic model, which can be used to rationalise potential close interactions in the other structures. The neutron structure of 5 confirms the existence of C–H···S hydrogen bonds, with the H···S distance falling well within the sum of the van der Waals radii of the atoms. The close-packing in 5–7 is mediated solely through these weak interactions, with the size of the cations influencing the structures.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3CE42031K
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8QI00355F
Abstract: Monodispersed Cu and Ni nanoparticles are deposited over TiO 2 using a hetero-bimetallic coordination polymer for efficient photocatalytic water splitting.
Publisher: Elsevier BV
Date: 07-2012
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9DT04606B
Abstract: A Co( ii ) coordination polymer shows SMM behaviour with an effective barrier height among the highest reported for such materials.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT11905F
Abstract: The nucleophilic addition of methanol and water to the dicyanonitrosomethanide anion, resulting in the formation of cyano(imino(methoxy)methyl)nitrosomethanide (cmnm) and carbamoylcyanonitrosomethanide (ccnm), respectively, is used as a means of in situ ligand synthesis during the formation of [Dy(8)(OH)(6)(OMe)(6)(cmnm)(10)(ccnm)(2)(H(2)O)(2)(MeOH)(2)] (1). This is the first time these reactions have been observed to be promoted by the presence of a lanthanoid ion. The core of the octanuclear cluster consists of two cubane moieties ([Dy(4)(OH)(3)(OMe)]), bridged by four methoxide ligands to form a central [Dy(8)(OH)(6)(OMe)(6)] moiety. The complex displays magnetic properties that are indicative of probable single molecule magnet features.
Publisher: Wiley
Date: 07-02-2011
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CE01133D
Abstract: A traditionally good chelating motif, propanediamine, has been incorporated into a robust coordination framework with vacant amine sites.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4CC00933A
Abstract: Polymorphic metal-organic framework (MOF) materials offer a platform for small-scale separation of complex mixtures of polycyclic aromatic hydrocarbons (PAHs) and polar compounds. Retention factors show dependence on both analyte dimensions and polarity, suggesting mixed-mode separation, allowing complete resolution of some analytes from multi-component mixtures.
Publisher: MDPI AG
Date: 28-06-2020
Abstract: The reliable and predictable synthesis of enantiopure coordination cages is an important step towards the realization of discrete cages capable of enantioselective discrimination. We have built upon our initial report of a lantern-type helical cage in attempts to expand the synthesis into a general approach. The use of a longer, flexible diacid ligand results in the anticipated cage [Cu4(L1)4(solvent)4] with a similar helical pitch to that previously observed and a cavity approximately 30% larger. Using a shorter, more rigid ligand gave rise to a strained, conjoined cage-type complex when using DABCO as an internal bridging ligand, [{Co4(L2)4(DABCO)(OH2)x}2 (DABCO)]. The expected paddlewheel motif only forms for one of the Co2 units within each cage, with the other end adopting a “partial paddlewheel” with aqua ligands completing the coordination sphere of the externally facing metal ion. The generic approach of using chiral diacids to construct lantern-type cages is partially borne out, with it being apparent that flexibility in the core group is an essential structural feature.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT00023G
Abstract: An integrated suite of synthesis and characterisation techniques that includes synchrotron-based single crystal, powder X-ray diffraction, nuclear magnetic resonance and electron diffraction have been employed to uncover two new distinct structures in the Ca(x)Ba(2-x)P(2)O(7) polymorphic phosphate system. These materials have particular relevance for their application as both biomaterials and phosphors. Calcium barium pyrophosphate, CaBaP(2)O(7), was shown by a combination of spectroscopic and diffraction techniques to have two polymorphs distinct in structure from all of the five previously reported polymorphs of Ca, Sr and Ba pyrophosphate. A high temperature polymorph HT-CaBaP(2)O(7) prepared at 1200 °C is orthorhombic, of space group P(212121) with a = 13.0494 Å, b = 8.9677 Å, c = 5.5444 Å. A low temperature polymorph LT-CaBaP(2)O(7), prepared below 1000 °C, is monoclinic with space group P2(1)/c and dimensions a = 12.065 Å, b = 10.582 Å, c = 9.515 Å, β = 94.609°.
Publisher: Elsevier BV
Date: 06-2017
DOI: 10.1016/J.CHROMA.2017.04.037
Abstract: A precursor solution to the metal-organic framework (MOF), Cd(1,4,7,10-tetrakis(4-carboxybenzyl)-1,4,7,10-tetraazacyclododecane), was aged in a surface-functionalised 250μm-diameter capillary, to generate a film containing the constituents of the bulk phase crystalline material. EDX analysis revealed a higher ratio of ligand elements (C, N and O) to Cd in the capillary coated phase compared to that achieved from bulk synthesis in a vial. Separation performance of the coated capillary for gas chromatography (GC) was compared to the performance of the original MOF crystals packed in tips for liquid elution chromatography (LEC) towards the separation of polycyclic aromatic hydrocarbons (PAHs) and small probe analytes with different properties. This study showed that different retention mechanisms were observed for the same set of analytes in gas and liquid phases. Independently of the trend of vapour pressure difference, the GC result showed less specific size selective retention, but with stronger retention towards larger PAHs. A linear solvation energy relationship correlation further revealed enhanced retention contributions (positive stationary phase descriptor values) by cavity formation/dispersion interactions and H-bonding with acid functionality of the probe analytes in both GC and LEC (though stronger in LEC), whilst H-bonding with basic functional groups slightly increased retention in GC retention was strengthened by dipole-dipole/dipole-induced dipole interactions only in LEC.
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B708589C
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B800339D
Abstract: A flexible capsule has been designed in which the anion-binding preorganisation is enhanced by a urea 'zipper'.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0CE01620A
Abstract: Flexible amine-functionalised tetracarboxylate ligands with different length arms generate a large variety of coordination polymers which notably lack topological consistency.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3CC48802K
Abstract: A reproducible metallocyclic motif containing amino-acid functionalised aromatic diimides has been employed to demonstrate remarkable control over entanglement topologies.
Publisher: Wiley
Date: 21-12-2009
Publisher: Elsevier BV
Date: 06-2008
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B707709B
Abstract: The formation of discrete complexes [M(mcoe)2S2] (M = Cu, Ni S = MeOH, H2O) vs. a nitroso-bridged ferromagnetically-coupled Cu(II) coordination polymer [Cu(mcoe)2] is influenced by the use of solvothermal reaction conditions.
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH16648
Abstract: A variety of transition metal complexes involving picolylcyanoacetamides (pica = NCCH2CONH-R R = 2-picolyl- (2pica), 3-picolyl- (3pica), 4-picolyl- (4pica)) and thiocyanate have been synthesised and their solid-state structures have been determined. The complexes were all obtained from reactions between the corresponding metals salts and pica ligands with sodium thiocyanate under ambient conditions. Both 3pica and 4pica coordinate to the metal solely through the nitrogen atom of the picolyl group and form discrete tetrahedral [M(NCS)2(pica)2] (3pica M = Mn, Zn 4pica M = Co) and octahedral [M(NCS)2(3pica)4] (M = Co, Fe, Ni) complexes. In addition, one-dimensional N,S-thiocyanate-bridged coordination polymers poly-[M(µ-NCS)2(pica)2] (3pica M = Cd 4pica M = Co, Cd) were obtained. The ligand 2pica gave the discrete octahedral complexes [Co(NCS)2(2pica)2] and [Cd(NO3)2(2pica)2] in which 2pica chelates in a bidentate fashion through its picolyl and carbonyl groups. Magnetic susceptibility measurements on the cobalt(ii) complexes were performed and showed short-range antiferromagnetic coupling for the [Co(NCS)2(4pica)2]n 1D polymer.
Publisher: American Chemical Society (ACS)
Date: 05-10-2017
DOI: 10.1021/ACS.INORGCHEM.7B02028
Abstract: A silver thiazolylurea complex, [Ag(TUTh)
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2CE26052B
Publisher: Elsevier BV
Date: 09-2021
Publisher: Wiley
Date: 26-03-2007
Abstract: The dimeric complex [Li(Ph2pz)(OEt2)]2 (1) and tetrameric cluster [Na(Ph2pz)(thf)]4 (2) were prepared by treatment of alkali-metal reagents (nBuLi and Na{N(SiMe3)2}, respectively) with 3,5-diphenylpyrazole (Ph2pzH) in Et2O (1) or THF (2). The polymer [Na(tBu2pz)]n (3) was obtained from reaction at elevated temperature in a sealed tube between Na metal and 3,5-di-tert-butylpyrazole (tBu2pzH). The complex [Na4(tBu2pz)2(thf)3(obds)]2 (4 obds = (OSiMe2)2O) was obtained as a minor product from prolonged treatment of tBu2pzH with elemental sodium in a silicone-greased flask. All four alkali-metal pyrazolato complexes were characterized by IR and 1H NMR spectroscopy and X-ray crystallography.The Li dimer 1 displays mu-eta(2):eta(1) lithium-pyrazolato binding, in which both lithium atoms are four-coordinate. Room- and variable-temperature NMR studies (1H, 13C, and 7Li) of 1 suggest similar behavior in solution, with peaks coalescing at low temperatures. Complexes 2 and 4 display distorted cubane structures. In 2, all the sodium atoms are five-coordinate, whereas 4 contains two sodium yrazolate/thf clusters (4:2:3 ratio) bridged by two obds(2-) units, as well as two four-coordinate and two five-coordinate sodium atoms. Compound 3 is composed of two independent chains with the unusual coordination modes mu3-eta(5):eta(2):eta(2), mu3-eta(5):eta(2):eta(1), and mu3-eta(4):eta(2):eta(1), with five-, six-, and seven-coordinate sodium atoms. Two oxo-centered M8 cage complexes [(tBu2pz)6Li8O] (5) and [(tBu2pz)6Na8O] (6) were obtained as by-products from attempted preparation of [Li(tBu2pz)] and [Na(tBu2pz)], respectively, and their structures were determined.
Publisher: CSIRO Publishing
Date: 2014
DOI: 10.1071/CH14191
Abstract: Reactions of 8-hydroxyquinoline (HOQ) with elemental rare-earth and transition metal combinations or alloys at 200–300°C yielded a variety of complexes, albeit in very low yields, including two structurally characterised homometallic complexes containing an unexpected biquinolinolate ligand. Reaction of HOQ with SmCo5 alloy gives rise to the complexes [SmCo2(OQ)7] (1), [Co4(OQ)4(BQ)2] (2), and [Sm3(OQ)5(BQ)2(H2O)] (3Sm), where BQ is 2,7′-biquinoline-8,8′-diolate, resulting from an unusual coupling reaction between two OQ/HOQ species at the 2 and 7′ positions. Complexes 1–3 and HOQ co-crystal 2·2HOQ were isolated as single crystals from separate reactions although formation of other products under the reaction conditions used was likely. Analogues of 3Sm with erbium and ytterbium were obtained using respective rare-earth metal filing in combination with nickel powder. Reaction involving cobalt powder only, without any rare-earth metals, yielded a homoleptic complex containing only the 8-quinolinolate ligand i.e. [Co4(OQ)8] (4). These results highlight the rewards, in terms of rich synthetic chemistry, and pitfalls, in terms of yield and isolation, of the pseudo-solid state synthetic approach using 8-quinolinolate ligands.
Publisher: American Chemical Society (ACS)
Date: 14-07-2009
DOI: 10.1021/JA9041912
Abstract: An unprecedented 2.5 nm array of pi interactions between eight aromatic rings drives the formation of a [2]catenane. Disruption of this array through the use of longer ligands results in the formation of only single, uncatenated rings. The catenated complex is shown to persist in solution alongside its constituent metallomacrocycles.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CE00149A
Abstract: Short and sterically encumbered pyrazole ligands have led to the first ex les of non-interpenetrated, dichromate pillared hybrid ultramicroporous materials.
Publisher: Wiley
Date: 27-05-2019
Abstract: A chiral, octahedral M
Publisher: Wiley
Date: 02-01-2007
Publisher: Wiley
Date: 08-05-2009
Abstract: New balls please! The viability of using carbonate as the primary anion in cluster formation is demonstrated in the synthesis of 'lanthaballs', spherical tridecanuclear lanthanoid complexes with a novel [Ln(CO(3))(6)] moiety in a [Ln(13)(CO(3))(14)] core (see picture). The chirality of the lanthaballs is evidenced in the configuration of extended columns of pi-stacked phenanthroline ligands. The structural and magnetic properties of lanthaballs are investigated.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4RA00241E
Abstract: An unusual, chloride-capped M 4 L 4 complex has been prepared using heterotopic ligands with carboxylate and dipyridyl coordinating sites.
Publisher: Wiley
Date: 08-08-2013
Abstract: A series of urea-derived heterocycles, 5N-substituted hexahydro-1,3,5-triazin-2-ones, has been prepared and their structures have been determined for the first time. This family of compounds only differ in their substituent at the 5-position (which is derived from the corresponding primary amine), that is, methyl (1), ethyl (2), isopropyl (3), tert-butyl (4), benzyl (5), N,N-(diethyl)ethylamine (6), and 2-hydroxyethyl (7). The common heterocyclic core of these molecules is a cyclic urea, which has the potential to form a hydrogen-bonding tape motif that consists of self-associative R₂²(8) dimers. The results from X-ray crystallography and, where possible, Laue neutron crystallography show that the hydrogen-bonding motifs that are observed and the planarity of the hydrogen bonds appear to depend on the steric hindrance at the α-carbon atom of the N substituent. With the less-hindered substituents, methyl and ethyl, the anticipated tape motif is observed. When additional methyl groups are added onto the α-carbon atom, as in the isopropyl and tert-butyl derivatives, a different 2D hydrogen-bonding motif is observed. Despite the bulkiness of the substituents, the benzyl and N,N-(diethyl)ethylamine derivatives have methylene units at the α-carbon atom and, therefore, display the tape motif. The introduction of a competing hydrogen-bond donor/acceptor in the 2-hydroxyethyl derivative disrupts the tape motif, with a hydroxy group interrupting the N-H···O=C interactions. The geometry around the hydrogen-bearing nitrogen atoms, whether planar or non-planar, has been confirmed for compounds 2 and 5 by using Laue neutron diffraction and rationalized by using computational methods, thus demonstrating that distortion of O-C-N-H torsion angles occurs to maintain almost-linear hydrogen-bonding interactions.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT31101A
Abstract: The synthesis of two high nuclearity lanthanoid clusters demonstrates the versatility of the carbonate anion as a robust cluster forming agent, potentially allowing for the formation of otherwise inaccessible core topologies. The complexes, [Gd(14)(CO(3))(13)(ccnm)(9)(OH)(H(2)O)(6)(phen)(13)(NO(3))](CO(3))(2.5)·(phen)(0.5) (1) and [Dy(14)(CO(3))(13)(ccnm)(10)(OH)(H(2)O)(6)(phen)(13)](CO(3))(2.5)·(phen)(0.5) (2) (ccnm = carbamoylcyanonitrosomethanide, phen = 1,10-phenanthroline), contain a [Ln(14)(CO(3))(13)(OH)] core in which the carbonate anions display four unique coordination modes. The complexes are chiral, and the ccnm ligands also display four unique coordination modes. Extensive intra- and intermolecular π-π stacking between phen ligands leads to the formation of 1D chains in the crystal structure. Both complexes display magnetic properties that are indicative of antiferromagnetic coupling, with complex displaying behaviour consistent with possible single molecule magnet properties.
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3CE41538D
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B715135G
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7CE00498B
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1QI01457A
Abstract: Enantiomeric selectivity is shown within the pores of a 1D coordination polymer, dependent on the nature of the pore space.
Publisher: CSIRO Publishing
Date: 2009
DOI: 10.1071/CH09224
Abstract: The synthesis, structure, and magnetism is reported for an antiferromagnetically coupled, disc-shaped cluster containing the anionic ligand carbamoylcyanonitrosomethanide (ccnm), [Fe8O6(MeO)6(ccnm)6], with an FeIII8O3 core.
Publisher: MDPI AG
Date: 04-03-2014
DOI: 10.3390/CRYST4010053
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4CE00816B
Publisher: American Chemical Society (ACS)
Date: 26-09-2016
DOI: 10.1021/ACS.INORGCHEM.6B01713
Abstract: A new ergent homopiperazine-derived ligand N,N'-bis(4-carboxyphenyl)-1,4-diazacycloheptane H
Publisher: American Chemical Society (ACS)
Date: 30-07-2014
DOI: 10.1021/CM502189C
Publisher: American Chemical Society (ACS)
Date: 21-01-2006
DOI: 10.1021/JO052339F
Abstract: Tripodal tris(urea) cationic receptors 1 and 2 containing p-tolyl or octyl substituents, respectively, have been synthesized, and their association behavior with anionic guests has been studied via a variety of methods. The receptors are based around a hexasubstituted aryl core and contain both urea and pyridinium functionalities. For 1:1 complexes, anions reside within the central cavity of the host species, held by hydrogen bonds from both NH and CH donors. The following host-anion complexes have been characterized by X-ray crystallography: 1-(Br)3, 1-(PF6)3.2(CH3)2CO, and 1-(NO3)1.5(PF6)1.5. Each structure contains the receptor in a significantly different geometry, highlighting the anion-dependent conformational flexibility of 1. Solution 1H NMR spectroscopic titrations have shown the two host species to display significant affinity for both halides and hydrogen sulfate and strongly suggest the persistence of CH...X- interactions despite the presence of "stronger" NH donor groups. Variable-temperature 1H NMR studies on the more soluble octyl derivative 2 show that there is a distinct change in conformation associated with the formation of a 1:1 host/guest complex. Computations using density functional theory (with the B3LYP functional) have been employed to aid in understanding the geometry of the 1:1 host/chloride complexes of 1 and 2. These experiments suggest that the lowest energy conformation for 1-Cl is one in which the ureidopyridinium arms are orientated upward forming a cavity that is sealed by CH...pi interactions, effectively forming a unimolecular capsule, whereas for 2 a less symmetrical "2-up, 1-down" geometry is favored.
Publisher: American Chemical Society (ACS)
Date: 12-10-2016
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5CC07422C
Abstract: Enantiomeric cages have supramolecular chirality induced by the chemical chirality of the ligands. Diastereomeric ligands or achiral ligands yields analogous centrosymmetric complexes.
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B700980A
Publisher: Elsevier BV
Date: 2020
Publisher: Wiley
Date: 08-09-2014
Abstract: A series of soluble metal ethylxanthate compounds was synthesised as precursors for metal sulfide thin films to be deposited using solution‐based techniques. Initially, a range of air‐ and moisture‐stable organic ethylxanthate (EtXn) salts were synthesised (cation=Me 4 N ( 1 ), Et 4 N ( 2 ), Pr 4 N ( 3 ), Ph 4 P ( 4 ), guanidinium ( 5 ), NMeH 3 ( 6 ), NMe 2 H 2 ( 7 ), NMe 3 H ( 8 ), NH 4 ( 9 )). Thermogravimetric analysis (TGA) was used to examine their decomposition profiles, which in turn informed the decision of which counter cation was best suited for inclusion in the metal xanthate compounds. Periodic NMR spectroscopy studies and single‐crystal X‐ray diffraction (SXRD) were used to determine the role protic ammonium counter cations play in the detrimental conversion of xanthates to dithiocarbamate anions. The organic salts 1 and 4 were used to form the metal ethylxanthate compounds (Me 4 N)[M(EtXn) x ] ( x =3 for M=Cd ( 10 Cd ), Ni ( 10 Ni ), Zn ( 10 Zn ) x =4 for M=La ( 11 La )) and (Ph 4 P)[M(EtXn) 3 ] (M=Cd ( 12 Cd ), Ni ( 12 Ni ), Zn ( 12 Zn )). Solubility studies on these compounds were performed using a range of solvents to demonstrate the viability of using these compounds for solution‐based deposition methods for thin‐film formation. TGA of the metal xanthate compounds was used to examine their thermal‐decomposition profiles and the product resulting from thermolysis was found to be the respective metal sulfide. In addition, the coproducts of thermal decomposition were analysed by headspace gas‐chromatography mass spectrometry (HS GC–MS) to probe the decomposition mechanism of the precursors. In situ variable‐temperature synchrotron XRD studies on both bulk and thin‐film s les of 10 Cd and 12 Cd were used to examine metal sulfide crystalline phase formation. Decomposition of both precursors was found to give CdS in a hexagonal phase, with the addition of CdCl 2 found to aid in increasing the crystallite size during crystallisation.
Publisher: Elsevier BV
Date: 2010
Publisher: Wiley
Date: 06-2010
Abstract: The anionic dinitrile ligand dicyanonitrosomethanide (dcnm), C(CN) 2 (NO) – , and the anion resulting from its addition product with water, carbamoylcyanonitrosomethanide (ccnm), C(CN)(CONH 2 )(NO) – , have been incorporated into lanthanoid complexes and display unusual η 2 (N,O) nitroso coordination modes. (Et 4 N) 3 [Ln(ccnm) 6 ] ( 1Ln 1Ln = 1La , 1Ce , 1Pr , 1Nd , 1Sm ) and (Me 4 N) 3 [Ln(ccnm) 6 ] ( 2Ln 2Ln = 2La , 2Ce , 2Pr , 2Nd ) are systems containing 12‐coordinate homoleptic trianionic lanthanoidate complexes. The nitroso groups of the ccnm ligands form three‐membered ring chelates with the lanthanoid metal centre, with the asymmetry of the nitroso η 2 interactions dependent upon the intramolecular N–H ··· O=N hydrogen bonding. Additional intermolecular hydrogen bonding interactions exist between adjacent amide and nitrile groups giving rise to 3D α‐Po and 6,8‐connected (4 12 .6 3 )(4 20 .6 8 ) networks in 1Ln and 2Ln , respectively. The compounds (Me 4 N) 3 [Ln(dcnm) 6 ] ( 3Ln 3Ln = 3La , 3Ce , 3Nd , 3Sm ) also contain a 12‐coordinate trianionic lanthanoidate complex with the nitroso group exhibiting a highly symmetrical η 2 interaction. The sterically crowded environments of [Ln(18‐crown‐6)(dcnm) 3 ] ( 4Ln 4Ln = 4La , 4Ce , 4Pr , 4Nd ) result in a shift towards a more asymmetric η 2 bonding of the nitroso group with decrease in the Ln 3+ radius. There is a corresponding increase of the Ln–O–N angle, and one ligand is η 1 (O) binding in 4Nd . The dcnm ligands in the discrete complexes [La(phen) 3 (dcnm) (3– x ) Cl x ], x ≈ 0.25 ( 5 ) (phen = 1,10‐phenanthroline), (Et 4 N)[Ce(phen) 2 (dcnm) 4 ] ( 6a / b , 6c ) and [Ce(phen) 2 (dcnm)Cl 2 H 2 O] ( 7 ) display a variety of coordination modes. Complex 5 has 1D chains formed by π–π stacking of adjacent phen co‐ligands. Complexes 6 contain the monoanionic complex [Ce(phen) 2 (dcnm) 4 ] – with two geometric isomers present in the crystal structure of 6a / b . Complex 7 forms extended 1D chains via hydrogen bonding between coordinated water and chloride atoms and an extensive array of face‐to‐face π interactions.
Publisher: Elsevier BV
Date: 06-2019
DOI: 10.1016/J.JCIS.2019.03.018
Abstract: The dearth of an efficient, robust, abundant and cost-effective water oxidation catalyst is debatably the major hurdle for the technological advancement of artificial photosynthesis devices. Herein, a three dimensional (3D) cobalt-based coordination polymer {[Co
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B905970A
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3CE42141D
Publisher: CSIRO Publishing
Date: 2017
DOI: 10.1071/CH16547
Abstract: A series of rare earth 3-(4′-methylbenzoyl)propanoate (mbp–) complexes [RE(mbp)3(H2O)] (RE = rare earth = Y, La, Ce, Nd, Ho, Er) have been prepared by either metathesis reactions between the corresponding rare earth chloride and Na(mbp) or protolysis of rare earth acetates by the free acid. Single-crystal X-ray diffraction studies of [RE(mbp)3(H2O)] (RE = Ce, Nd) and [Ce(mbp)3(dmso)] reveal a 1D carboxylate-bridged polymeric structure in the solid state, featuring 9-coordinate rare earth ions. X-ray powder diffraction patterns of the bulk materials indicates that all of the [RE(mbp)3(H2O)] complexes except RE = La are isomorphous. Hence, there is no structural change from the complex with RE = Ce to that with RE = Er despite the lanthanoid contraction. The 1H NMR spectra of the RE = Ho or Er complexes in (CD3)2SO show large paramagnetic shifts and broadening of the CH2 resonances, indicating the retention of substantial carboxylate coordination in solution.
Publisher: American Chemical Society (ACS)
Date: 22-04-2010
DOI: 10.1021/CG900783K
Publisher: Wiley
Date: 03-2009
Publisher: Springer Berlin Heidelberg
Date: 15-12-2003
DOI: 10.1007/B14138
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CC03737J
Abstract: The first cadmium-based ionic liquids (ILs) have been developed, along with a family of cadmium dialkyldithiocarbamate salts, (cation)[Cd(R 2 dtc) 3 ], in the pursuit of single source molecular precursors that thermolyse to form cadmium sulfide.
Publisher: Wiley
Date: 09-12-2020
Publisher: American Chemical Society (ACS)
Date: 11-09-2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4CE02547D
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2DT02616C
Abstract: A series of mononuclear lanthanoidate complexes isolated as [Bu
Publisher: Elsevier BV
Date: 11-2019
Publisher: Royal Society of Chemistry (RSC)
Date: 2007
DOI: 10.1039/B705202B
Abstract: Metathesis reactions of the alkali metal formamidinates M(RNC(H)NR), M = Li or K R = C(6)H(3)-2,6-Pr(i)(2) (L(1)), C(6)H(3)-2,6-Et(2) (L(2)) C(6)H(2)-2,4,6-Me(3) (L(3)), C(6)H(3)-2,6-Me(2) (L(4)) or C(6)H(4)-2-Ph (L(5)), with BiX(3) (X = Cl or Br) gave a range of bismuth(iii) formamidinate complexes [Bi(L)Br(micro-Br)(thf)](2) (L = L(1), L(4)), [{Bi(L(1))Cl(2)(thf)}(2)Bi(L(1))Cl(2)], [Bi(L)(2)X] (L = L(2), L(5), X = Br L = L(1), X = Cl), and [Bi(L)(3)] (L = L(2), L(3)). An analogous organometallic complex Bi(L(1))(2)Bu(n) was also isolated as a side product in one instance. Structural characterisation of the di-halide complexes show symmetrical dimers for X = Br, with two bromide bridges, and a coordinated thf molecule on each Bi atom, whereas for X = Cl a thf deficient species was crystallised, and has a weakly associated trinuclear array with two coordinated thf molecules per three Bi atoms. Complexes of the form Bi(L)(2)X (X = Br, Cl, Bu(n)) and Bi(L)(3) all have monomeric structures but the Bi(L)(3) species show marked asymmetry of the formamidinate binding, suggesting that they have reached coordination saturation.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0DT01725F
Abstract: A series of polynuclear mixed-ligand tris(pyrazolyl)methane iron(II) complexes displaying high temperature spin crossover behaviour has been synthesised. These complexes are of the type [(Fe((3,5-Me(2)pz)(3)CH))(n)(μ-L)](BF(4))(2n), where μ-L is one of five bridging ligands X(CH(2)OCH(2)C(pz)(3))(n), (X = the central linking moiety, pz = pyrazolyl ring and n = 2 (ditopic), 3 (tritopic) or 4 (tetratopic)). Throughout the series the terminal tris(3,5-dimethylpyrazolyl)methane co-ligand (3,5-Me(2)pz)(3)CH and the BF(4)(-) counter anion were kept constant while variations in the central linking moiety have produced three dinuclear complexes and a trinuclear and tetranuclear complex, all isolated as solvates. The three dinuclear complexes are a 1,4-xylene-bridged complex 1·2DME, a 2,6-naphthalene-bridged complex 2·2.5MeCN.2DME and a 1,4-butene-bridged complex 3·2DME. The trinuclear complex 4·solvent (solvent undefined) has a 1,3,5-mesitylene core and the tetranuclear complex, 5·8MeCN.2(t)BuOMe, has a 1,2,4,5-tetramethylbenzene core (DME = dimethoxyethane, (t)BuOMe = tertiarybutyl-methylether). The trinuclear cluster has a "3-up" cup shape with the cups arranging themselves in pairs to form capsules that contain anion guests. All the solvated compounds have been structurally characterised and both the solvated and desolvated versions have had their magnetic and thermal properties thoroughly investigated by variable temperature magnetic susceptibility, differential scanning calorimetric and Mössbauer spectral methods. They all display typical low spin iron(II) magnetic behaviour at room temperature and all undergo a spin state transition to high spin iron(II) above room temperature. In particular, complex 1·2DME shows an abrupt spin transition which shifts, upon desolvation, to a lower value of T(1/2) and in addition displays a small thermal hysteresis.
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B913234A
Abstract: A series of iron(III) 1-D polymeric materials of the general formula [Fe(III)(Schiff-base)(L)](BPh(4)).n(CH(3)OH) (Schiff base = N,N'-ethylenebis(salicylaldimine) (H(2)salen), N,N'-o-phenylenebis(salicylaldimine) (H(2)salophen) and N,N'-ethylenebis(acety1acetone)-2,2'-imine (H(2) acen) L = bridging di-pyridyl or di-imidazole ligand, n = 0-4) and analogues therein, have been synthesised and structurally and magnetically characterised. In this series, a range of structural motifs are observed including linear 1-D chains, hydrogen-bonded chains, a 'hybrid' 1-D chain- and -dimer compound and a hydrogen-bonded dinuclear material all exhibit extensive intermolecular interactions. The magnetic consequences of varying both the equatorial Schiff-base ligands and axial bridging ligands have been investigated. Overall, we find that, independent of the axial bridging ligand employed, the salen equatorial ligand results in a high spin character and the acen ligand results in spin crossover character, generally with a spin transition of a gradual nature. Variations in magnetic behaviour can be rationalized, in part, in terms of the C(2)N(2) backbone conformation of the equatorial Schiff base ligand, which may either inhibit or allow a spin transition.
Publisher: American Chemical Society (ACS)
Date: 25-05-2007
DOI: 10.1021/OM0701571
Publisher: Royal Society of Chemistry (RSC)
Date: 2008
DOI: 10.1039/B711891K
Publisher: Swiss Chemical Society
Date: 26-06-2013
Abstract: Small cyano anions, and their derivatives, have proved to be remarkably versatile building blocks for coordination polymers. They have led to magnetically ordered materials, structures with new entangled motifs or novel topologies, and a significant structural ersity, including polymorphism, induced by subtle changes in anion, cation, co-ligands, preparative conditions, or even desolvation.
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3DT01378B
Abstract: Cubic coordination cages encapsulate P–F containing guests and, when complexed, protect the P–F bond from aqueous hydrolysis.
Publisher: CSIRO Publishing
Date: 2013
DOI: 10.1071/CH13185
Abstract: Three new zinc 8-quinaldinolate complexes have been obtained from rearrangement reactions at elevated temperatures including the first homoleptic zinc 8-quinaldinolate complex. The homoleptic, trinuclear complex [Zn3(MQ)6] (1) (MQ = 8-quinaldinolate) was obtained by the recrystallisation of amorphous Zn(MQ)2 from a 1,2,4,5-tetramethylbenzene flux at 270°C. The heteroleptic complexes [Zn4Cl4(MQ)4] (2) and [Zn4Cl2(MQ)6] (3) were simultaneously obtained by the reaction between Zn(MQ)2 and anhydrous ZnCl2 under the same conditions. All complexes contain quinaldinolate ligands in a mixed chelating–bridging coordination mode. The homoleptic complex adopts a V-shaped geometry whereas the heteroleptic complexes adopt closely related cyclic structures.
Publisher: American Chemical Society (ACS)
Date: 07-01-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0GC03999C
Abstract: Furfural can be electrochemically hydrogenated to 2-methylfuran in mild conditions with high selectivity using a catalyst containing single atom copper active sites and oxophilic phosphorus dopants.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1DT11369K
Abstract: Several new first-row transition-metal complexes have been synthesised by combining the polynitrile dianion HCTMCP(2-) (hexacyanotrimethylenecyclopropandiide) with neutral, chelating co-ligands 2,2'-bipyridine, 1,10-phenanthroline and 3-(2-pyridyl)pyrazole. The products cover a remarkable range of species including mononuclear complexes, dimers, charge-separated species and coordination polymers. Complexes containing 2,2'-bipyridine take the form [Mn(2,2'-bipy)(2)(HCTMCP)](2)·2MeOH (1) or [M(2,2'-bipy)(3)](HCTMCP) (2Fe and 2Co) which are dimeric and charge-separated products, respectively. The products obtained using 1,10-phenanthroline were the discrete complex [Co(HCTMCP)(1,10-phen)(2)(H(2)O)]·H(2)O·MeCN (3) and the 1D coordination polymer [Mn(HCTMCP)(1,10-phen)(H(2)O)(MeOH)] (4). Complexes using the 3-(2-pyridyl)pyrazole co-ligand (pypzH) form similar 1D complexes to 4, namely [Mn(pypzH)(HCTMCP)(MeOH)(H(2)O)] (5) and [M(pypzH)(HCTMCP)(MeOH)(2)] (6Co and 6Fe), albeit with different hydrogen-bonding motifs between the chains. The polymeric HCTMCP complexes show weak to zero antiferromagnetic coupling between metal centres and thus no long-range ordering.
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B814158D
Publisher: Royal Society of Chemistry (RSC)
Date: 2004
DOI: 10.1039/B415627G
Publisher: Wiley
Date: 21-06-2023
Abstract: Owing to the strict hard/soft dichotomy between the lanthanoids and tellurium atoms, and the strong affinity of lanthanoid ions for high coordination numbers, low‐coordinate, monomeric lanthanoid tellurolate complexes have remained elusive as compared to the lanthanoid complexes with lighter group 16 elements (O, S, and Se). This makes the development of suitable ligand systems for low‐coordinate, monomeric lanthanoid tellurolate complexes an appealing endeavor. In a first report, a series of low‐coordinate, monomeric lanthanoid (Yb, Eu) tellurolate complexes were synthesized by utilizing hybrid organotellurolate ligands containing N‐donor pendant arms. The reaction of bis[2‐((dimethylamino)methyl)phenyl] ditelluride, 1 and 8,8′diquinolinyl ditelluride, 2 with Ln 0 metals ( Ln =Eu, Yb) resulted in the formation of monomeric complexes [ Ln II (TeR) 2 (Solv) 2 ] [R=C 6 H 4 ‐2‐CH 2 NMe 2 ] [ 3 : Ln =Eu, Solv=tetrahydrofuran 4 : Ln =Eu, Solv=acetonitrile 5 : Ln =Yb, Solv=tetrahydrofuran 6 : Ln =Yb, Solv=pyridine] and [Eu II (TeNC 9 H 6 ) 2 (Solv) n ] ( 7 : Solv=tetrahydrofuran, n=3 8 : Solv=1,2‐dimethoxyethane, n=2), respectively. Complexes 3 – 4 and 7 – 8 represent the first sets of ex les of monomeric europium tellurolate complexes. The molecular structures of complexes 3 – 8 are validated by single–crystal X‐ray diffraction studies. The electronic structures of these complexes were investigated using Density Functional Theory (DFT) calculations, which revealed appreciable covalency between the tellurolate ligands and lanthanoids.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2CE00269H
Abstract: High connectivity octacarboxylate ligands containing non-coordinating diamine cores lead to a wide variety of new MOFs, many containing cage-like pores.
Publisher: American Chemical Society (ACS)
Date: 09-10-2014
DOI: 10.1021/CG501004U
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9CE00371A
Abstract: Flexible tetrabenzoate xylylenediamine-based ligands form both discrete and polymeric assemblies, the latter displaying the targeted amine-lined pore spaces.
Publisher: Elsevier BV
Date: 06-2018
Publisher: International Union of Crystallography (IUCr)
Date: 12-01-2016
Publisher: Wiley
Date: 21-05-2019
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0CC00711K
Abstract: The desolvation of lattice methanol from between the 1D chains in {[Cu(4,4'-bipyridine)(ccnm)(2)].4MeOH} (ccnm = carbamoylcyanonitrosomethanide) under ambient conditions, a weight loss of 22.4%, results in a solid state conversion to the 3D network [Cu(4,4'-bipyridine)(ccnm)(2)].
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8CC09191A
Abstract: The formation of metallocatenanes, and their disruption by aromatic solvents, is followed by excimer and exciplex emission.
Publisher: American Chemical Society (ACS)
Date: 15-06-2011
DOI: 10.1021/IC200591U
Abstract: The first ex les of polymeric complexes that contain the polynitrile dianion hexacyanotrimethylenecyclopropanediide (HCTMCP(2-)) were isolated and their magnetic properties have been explored. Complexes of the form (n-TBA)(2)[M(HCTMCP)(2)(H(2)O)(2)] (1) (M = Mn(II), Fe(II), Co(II), Cd(II)) possess (4,4) sheet structures with large cavities that contain the tetra-n-butylammonium (n-TBA) countercations. Synthesis using sodium as the countercation yields a family of products with the general form [M(S)(4)M(S)(2)(HCTMCP)(2)] (S = EtOH, M = Fe(II) (2) S = MeOH, M = Co(II) or Zn(II) (3)). These complexes adopt a variety of two-dimensional (2D) structures. The complex [Mn(3)(HCTMCP)(2)(H(2)O)(12)](HCTMCP)·6(H(2)O) (4) contains cationic (6,3) sheets with the counteranion and solvent molecules encapsulated within the hexagonal windows. Complexes 1-4 display weak antiferromagnetic coupling in all cases. The first ex le of a complex that contains the CN-coordinated monoanionic radical HCTMCP (•-), [Cu(HCTMCP)(MeCN)(2)] (5) is described. This one-dimensional (1D) coordination polymer, containing tetrahedral Cu(I) centers, displays medium strength antiferromagnetic coupling that is mediated through π-interactions between the radical anions on adjacent chains.
Publisher: Wiley
Date: 27-11-2007
Abstract: The small dinitrile anion carbamoyldicyanomethanide, [C(CN)2-(CONH2)]- (cdm), reproducibly forms a hydrogen-bonded tape containing two different supramolecular synthons: a "heterotape". The tape incorporates both an amide dimer and a nitrile-containing ring. The robustness of the motif is confirmed by its persistence from an isolated tape in a separated ion-pair structure, [K(15c5)2](cdm) x H2O, to its incorporation into coordination complexes of octahedral metals, thus facilitating the formation of 2D sheets. Complexes containing coligands that occupy the equatorial coordination sites, [Cu(2,2'-py2NH)2(cdm)2] x 2 MeOH, [Ni(cyclam)(cdm)2], and [Cu(cyclam)(cdm)2] x 2 MeOH (cyclam = 1,4,8,11-tetraazacyclotetradecane, 2,2'-py2NH = di(2-pyridyl)amine), show retention of the heterotape motif, whilst the ethylene diamine complex [Cu-(en)2(cdm)2] (en = ethylene diamine) displays an alternative hydrogen-bonding motif due to interference from the diamine ligands.
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B512779C
Abstract: Two types of calix[4]arene derived hosts for anions with, respectively, 1,3-alternate and cone conformations have been prepared the 1,3-alternate system binds dicarboxylate anions in a ditopic manner while the cone compounds are deprotonated by carboxylates.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1CC05610G
Abstract: Self-sorting regimes are controlled by adjusting steric interactions in self-assembled coordination cages and equilibration followed by HPLC. Statistical or biased distributions can be obtained, including isolation of a single heteroleptic species.
Publisher: Elsevier BV
Date: 09-2009
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2ME00259K
Abstract: The interpenetrating 2D-sheet framework of Co-TMBT-MOF cast onto nickel foam is used as a pre-catalyst to generate an efficient OER catalyst with low overpotential.
Publisher: American Chemical Society (ACS)
Date: 17-07-2003
DOI: 10.1021/JA034921W
Abstract: The synthesis, anion binding, and conformational properties of a series of 3-aminopyridinium-based, tripodal, tricationic hosts for anions are described. Slow anion and conformational exchange on the (1)H NMR time scale at low temperature, coupled with NMR titration, results in a high level of understanding of the anion-binding properties of the compounds, particularly with respect to significant conformational change resulting from induced fit complexation. Peak selectivity for halides, particularly Cl(-), is observed. The approach has been extended to dipodal and tripodal podands based on 3-aminopyridinium "arms" containing photoactive anthracenyl moieties. The 1,3,5-tripodal host shows a remarkable selectivity for acetate over other anions, in contrast to the analogous unsubstituted tris(3-aminopyridinium) analogue, despite the fact that low-temperature (1)H NMR experiments reveal a total of four acetate-binding conformations. Photodimerization of anthracene units results in the formation of potential fluorescent anion sensors.
Publisher: Wiley
Date: 25-07-2014
Abstract: Effective separation of mixtures of enantiomers is of continuing interest in analytical and preparative chromatography, with new materials frequently designed and tested. We report two new enantiomerically pure 2D→3D interpenetrated materials used as stationary liquid chromatographic (LC) phases that are shown to resolve selected racemic mixtures with enantiomeric and chemical selectivity. Dicarboxylate ligands derived from amino acids on naphthalene and perylene cores form 2D frameworks that interpenetrate to give 3D structures. Selectivity is initially tested by uptake from solution subsequent LC methods show that the materials exhibit resolution of racemic analytes in 'micro-columns' and that the two closely related materials show markedly different selectivity for different analytes with much greater activity than the ligands alone. Comparison with a close-packed analogue suggests that the separation activity is largely due to surface effects.
Publisher: CSIRO Publishing
Date: 2020
DOI: 10.1071/CH19561
Abstract: The structural characterisation of bis(8-sulfanylquinolinium) hexachloridostannate(iv) (2) is reported and the variable reaction behaviour of this compound in different solvents has been explored. In particular, attempted recrystallization of 2 from chloroform and dichloromethane affords two polymorphs of cis-dichloridobis(8-quinolinethiolato)tin(iv), 3m and 3t, respectively. Attempted recrystallization of 2 from methanol gives crystals of 8,8′-dithiodiquinolinium hexachloridostannate(iv) 4. When 2 is dissolved in dimethyl sulfoxide in the presence of air, it undergoes oxidation to afford diquinolinyl-8,8′-disulfide 5. The molecular structures of the isolated compounds 2–4 are unambiguously authenticated by single crystal X-ray diffraction studies. The electronic structure properties of all the isolated compounds 2–4 are thoroughly studied by DFT calculations.
Publisher: American Chemical Society (ACS)
Date: 19-03-2014
DOI: 10.1021/CG500051M
Publisher: Informa UK Limited
Date: 10-09-2007
Location: United Kingdom of Great Britain and Northern Ireland
Start Date: 2012
End Date: 2016
Funder: Australian Research Council
View Funded ActivityStart Date: 02-2021
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Amount: $209,000.00
Funder: Australian Research Council
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Amount: $272,000.00
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End Date: 11-2018
Amount: $683,068.00
Funder: Australian Research Council
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End Date: 04-2018
Amount: $830,000.00
Funder: Australian Research Council
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End Date: 05-2022
Amount: $620,000.00
Funder: Australian Research Council
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End Date: 12-2017
Amount: $330,000.00
Funder: Australian Research Council
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End Date: 12-2027
Amount: $5,000,000.00
Funder: Australian Research Council
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