ORCID Profile
0000-0001-8250-3098
Current Organisation
La Trobe University
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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)
Analytical Chemistry | Sensor Technology (Chemical aspects) | Transition Metal Chemistry | Physical Chemistry (Incl. Structural) | Colloid And Surface Chemistry | Inorganic Chemistry | Organic Chemical Synthesis | Electroanalytical Chemistry | Analytical Spectrometry | Electrochemistry | Materials Engineering Not Elsewhere Classified | Catalysis and Mechanisms of Reactions | Physical Chemistry of Materials | Characterisation of Biological Macromolecules | Main Group Metal Chemistry | Optical Properties of Materials | Medicinal and Biomolecular Chemistry | Synthesis of Materials | Separation Science | Solid State Chemistry | Biomaterials | Bioinorganic Chemistry | Nanochemistry and Supramolecular Chemistry | F-Block Chemistry | Physical Organic Chemistry | Biochemistry and Cell Biology not elsewhere classified | Biological Physics | Physical Chemistry not elsewhere classified | Manufacturing Processes and Technologies (excl. Textiles) | Analytical Biochemistry | Condensed Matter Physics—Other
ANZSRC Socio-Economic Objective (SEO)
Expanding Knowledge in the Chemical Sciences | Scientific Instruments | Fabricated metal products not elsewhere classified | Plastic products (incl. Construction materials) | Other | Other | Chemical sciences | Ceramics, glass and industrial mineral products not elsewhere classified | Diagnostic Methods | Expanding Knowledge in the Physical Sciences | Expanding Knowledge in the Biological Sciences |
Related Links
Publications
Emission from the working and counter electrodes under co-reactant electrochemiluminescence conditions
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1SC01236C
Abstract: Exploration of potential-dependent, multi-colour co-reactant electrochemiluminescence from multiple luminophores at the working and counter electrodes reveals new pathways to emission.
Electrochemiluminescent Ruthenium(II) N-Heterocyclic Carbene Complexes: a Combined Experimental and Theoretical Study
Publisher: American Chemical Society (ACS)
Date: 18-06-2013
DOI: 10.1021/IC400263R
Abstract: A series of four Ru(II) complexes of the form [Ru(bpy)2(C(^)N)](2+) (where C(^)N is a bidentate pyridine-functionalized imidazolylidene- or benzimidazolylidene-based N-heterocyclic carbene (NHC) ligand and bpy is 2,2'-bipyridine) have been synthesized using a Ag(I) transmetalation protocol from the Ru(II) precursor compound, Ru(bpy)2Cl2. The synthesized azolium salts and Ru(II) complexes were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy, cyclic voltammetry, and electronic absorption and emission spectroscopy. The molecular structures for two benzimidazolium salts and three Ru(II) complexes were determined by single crystal X-ray diffraction. The complexes display photoluminescence within the range 611-629 nm, with the emission wavelength of the benzimidazolylidene containing structures, slightly blue-shifted relative to the imidazolylidene containing complexes. All complexes exhibited a reversible, one-electron oxidation, which is assigned to the Ru(2+/3+) redox couple. When compared to [Ru(bpy)3](2+), complexes of imidazolylidene containing ligands were oxidized at more negative potentials, while those of the benzimidazolylidene containing ligands were oxidized at more positive potentials. All four complexes exhibited moderately intense electrochemiluminescence (ECL) with the obtained ECL spectra closely resembling the photoluminescence spectra. The ability to predictably fine-tune the highest occupied molecular orbital (HOMO) level of the Ru(II) complexes via the flexible synthetic strategy offered by NHCs is valuable for the design of ECL-based multiplexed detection strategies.
Annihilation electrogenerated chemiluminescence of mixed metal chelates in solution: modulating emission colour by manipulating the energetics
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4SC02697G
Abstract: The emissions of the mixed annihilation ECL of metal complexes can be effectively predicted by estimations of reaction exergonicity.
Spectroscopy of Naphthalene Diimides and Their Anion Radicals
Publisher: CSIRO Publishing
Date: 2004
DOI: 10.1071/CH04130
Abstract: Naphthalene diimides 1–4 having different N,N-disubstitution undergo single electron reduction processes either chemically or electrochemically to yield the corresponding radical anion in high yield. This study concentrates on 1, bearing pentyl side chains connected through the diimide nitrogens, and compares the results obtained against those bearing isopropyl, propargyl, and phenylalanyl side chains. Compound 1 exhibits mirror image absorption and fluorescence in the near-UV region in CH2Cl2 and dimethylformamide that is typical of monomeric N,N-dialkyl-substituted naphthalene diimides. In toluene, excimer-like emission is observed, which suggests ground-state complexes involving 1 are formed. X-Ray crystallography has been used to characterize 1 in the solid state. Cyclic voltammetry enables the reversible potentials for [NDI]0/– and [NDI]−/2– type processes to be measured. Bulk one-electron reduction of 1–4 is characterized by dramatic changes in the absorption and emission spectra. Additionally, highly structured EPR (electron paramagnetic resonance) signals from dimethylformamide solutions of the radical anions of 1–3 have been obtained and are consistent with coupling between the unpaired electron and the naphthalene diimide nitrogens and hydrogens and the NCH hydrogens of the appropriate side chains. The overall structure of the EPR spectrum is substituent-dependent. These changes in spectroscopic output upon an electronic input may be described as a simple ‘on/off’ switching mechanism with which to apply a ‘bottom-up’ approach to molecular device manufacture.
Chemiluminescence from osmium(ii) complexes with phenanthroline, diphosphine and diarsine ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2AN35446B
Abstract: The reaction of various [Os(L)(2)(L')](2+) complexes (where L and L' are phenanthroline, diphosphine or diarsine ligands) and organic reducing agents after chemical or electrochemical oxidation of the reactants produces an emission of light corresponding to MLCT transitions. In certain instances, the emission was greater than that of [Ru(bipy)(3)](2+), but the relative signals were dependent on many factors, including reagent concentration, mode of oxidation, reducing agent and the sensitivity of the photodetector over the wavelength range.
The synthesis of novel core-substituted naphthalene diimides via Suzuki cross-coupling and their properties
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B9NJ00476A
Chemiluminescence from reactions with bis-cyclometalated iridium complexes in acidic aqueous solution
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B905024H
Abstract: Chemical reactions between certain bis-cyclometalated iridium complexes, cerium(IV) and organic reducing agents in aqueous solution produce an emission of light which in some cases is more intense than that from analogous reactions with conventional ruthenium-based reagents, thus providing a new avenue for chemically-initiated luminescence detection.
Electron Transfer-Induced cis−trans Isomerization of [Mn(CN)(CO)2{P(OPh)3}(Ph2PCH2PPh2)]: Solution and Solid State Voltamme
Publisher: American Chemical Society (ACS)
Date: 07-02-2003
DOI: 10.1021/JP027529Y
Co-reactant Electrogenerated Chemiluminescence of Iridium(III) Complexes Containing an Acetylacetonate Ligand
Publisher: Wiley
Date: 03-05-2017
Effect of Surface Immobilization on the Electrochemiluminescence of Ruthenium-Containing Metallopolymers
Publisher: American Chemical Society (ACS)
Date: 26-01-2006
DOI: 10.1021/AC0513919
Abstract: The effect of surface confinement on the electrochemiluminescence (ECL) properties of metallopolymer [Ru(bpy)2(PVP)10]2+, where bpy is 2,2'-bipyridyl and PVP is poly(4-vinylpyridine), is reported. Immobilizing a luminescent material on an electrode surface can substantially modulate its photophysical properties. Significantly, our study revealed that the overall efficiency of the ECL reaction for the metallopolymer film is almost four times higher, at 0.15%, than the highest value obtained for [Ru(bpy)2(PVP)10]2+ dissolved in solution, (phi(ECL) = 0.04%). Electrochemistry has been used to create well-defined concentrations of the quencher Ru3+ within the film. Analysis of both the steady-state luminescence and lifetimes of the film reveals that static quenching by electron transfer between the photoexcited Ru2+ and the Ru3+ centers is the dominant quenching mechanism. The bimolecular rate of electron transfer is (2.5 +/- 0.4) x 10(6) M(-1) s(-1). The implications of these findings for ECL-based sensors, in terms of optimum luminophore loading, is considered.
Iridium Complexes of N-Heterocyclic Carbene Ligands: Investigation into the Energetic Requirements for Efficient Electrogenerated Chemiluminescence
Publisher: American Chemical Society (ACS)
Date: 27-05-2014
DOI: 10.1021/OM500076W
Metathesis Reactions between Heavy d-8 Fluorides and I(III)–Pyridine Complexes
Publisher: American Chemical Society (ACS)
Date: 19-02-2020
Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications
Publisher: American Chemical Society (ACS)
Date: 07-2021
Photophysical and Electrochemical Properties of Phenanthroline‐Based Bis‐cyclometallated Iridium Complexes in Aqueous and Organic Media
Publisher: Wiley
Date: 22-09-2011
Electrochemical studies of porphyrin-appended dendrimers
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B516281E
Abstract: The electrochemical properties of porphyrin-appended dendrimers containing 2-, 4-, 8-, 16-, 32- and 64-porphyrin macrocycles in their free-base and zinc(II) forms have been investigated. Both series gave diffusional based voltammetric responses in dichloromethane. There was minimal effect of dendrimer generation on the redox potentials. Multiple pi-cation and anion radicals as well as dications and dianions were formed on the surface of the dendrimers on oxidation or reduction as appropriate, with each cyclic voltammetric wave representing electron transfer to or from multiple non-interacting porphyrin sites. Electrostatic interactions in the higher generation dendrimers result in kinetic effects being observed for the highly charged species generated when each porphyrin unit is doubly or triply oxidised. The number of electrons transferred on reduction or oxidation of the dendrimers was evaluated using steady-state microelectrode voltammetry. For the lower generations of species a good correlation was observed between numbers of electrons transferred and number of porphyrin entities per molecule for the dendrimers containing 32 and 64 units, however, slight negative deviations were observed, possibly due to electrostatic interactions as the porphyrins become closer packed.
Multi-colour bipolar electrochemiluminescence for heavy metal ion detection
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8CC08472F
Abstract: We report a new approach to heavy metal ion detection based on bipolar electrochemiluminescence (BP-ECL), which is simple and low cost yet highly sensitive.
Mobile Phone Based Electrochemiluminescence Detection in Paper-Based Microfluidic Sensors
Publisher: Springer New York
Date: 05-12-2014
DOI: 10.1007/978-1-4939-2172-0_19
Abstract: The development of simple, inexpensive paper-based sensors for medical diagnostics and other applications is now an important emerging area in the field of biosensors however, the electronic instrument or reader used to interrogate such sensors adds significantly to the cost of the analysis. In this chapter we describe the design and construction of novel, low-cost disposable electrochemiluminescent (ECL) sensors based on screen printed carbon electrodes and paper-based microfluidics. Moreover, a method to interrogate these sensors using only a mobile phone is articulated. This is realized by exploiting the audio output of the device to achieve electrochemical control, while using the camera to detect the resulting light emitted during the ECL reaction. The combination of cell phone technology with low-cost paper microfluidic sensors dramatically reduces the cost of sensing and has the potential to enhance health-care outcomes by exploiting the functionality, connectivity, and close to worldwide penetration of mobile phone technology.
Novel Electrochemiluminescent Platinum (II) Schiff-Base Complexes
Publisher: The Electrochemical Society
Date: 21-03-2011
DOI: 10.1149/1.3557872
Abstract: A series of platinum (II) complexes with Schiff base ligands were synthesized and compared in terms of their photoluminescence, electrochemical and electrochemiluminescence (ECL) properties. Photochemical and electrochemical techniques were used to establish the relationship between the photophysical and redox properties. The emission wavelengths (λem) of theses complexes were found to be highly tuneable with shifts of up to 150 nm in the emission resulting from very minor changes in the ligand structure. All reported complexes exhibit intense ECL via both annihilation and co-reactant pathways. The ECL properties are considered in the light of the photochemical and electrochemical properties of each complex as well as the thermodynamics of the ECL reaction in each case. The findings provide useful insights into the favorable characteristics required for efficient ECL and the directions which should be explored in the search for new ECL luminophores.
Use of a mobile phone for potentiostatic control with low cost paper-based microfluidic sensors
Publisher: Elsevier BV
Date: 08-2013
DOI: 10.1016/J.ACA.2013.06.005
Abstract: By exploiting its ability to play sounds, a mobile phone with suitable software installed can serve the basic functions of a potentiostat in controlling an applied potential to oxidise ECL-active molecules, while the resultant photonic signal is monitored using the camera in video mode. In combination with paper microfluidic sensors this opens significant new possibilities for low-cost, instrument-free sensing.
Intense near-infrared electrochemiluminescence facilitated by energy transfer in bimetallic Ir-Ru metallopolymers
Publisher: Elsevier BV
Date: 05-2021
Straightforward Determination of Homogeneous Kinetics Using Fourier Transform Alternating Current Voltammetry (Ftacv)
Publisher: Elsevier BV
Date: 2023
DOI: 10.2139/SSRN.4581261
Potential-controlled visible and near-infrared electrochemiluminescence from a BODIPY-DO3A macrocycle conjugate
Publisher: Elsevier BV
Date: 11-2023
Electrochemically Sensitized Luminescence from Lanthanides in d‐/f‐Block Heteronuclear Arrays
Publisher: Wiley
Date: 13-11-2017
Selective Excitation of Concomitant Electrochemiluminophores: Tuning Emission Color by Electrode Potential
Publisher: Wiley
Date: 21-03-2012
Highly Stable ECL Active Films Formed by the Electrografting of a Diazotized Ruthenium Complex Generated in Situ from the Amine
Publisher: American Chemical Society (ACS)
Date: 30-11-2010
DOI: 10.1021/LA104117H
Abstract: The electrodeposition of the electrochemiluminescent (ECL) ruthenium complex, bis(2,2'-bipyridyl)(4'-(4-aminophenyl)-2,2'-bipyridyl)ruthenium(II), [Ru(bpy)(2)(apb)](2+), via the in situ formation of a diazonium species from aqueous media is reported. Surface characterization undertaken using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) determined that the layer is bound to the substrate via azo bonding. The layer displays good ECL activity and is stable over a long period of time. The excellent potential of this system for ECL sensing applications is demonstrated using the well-known ECL coreactant 2-(dibutylamino)ethanol (DBAE) as a model analyte, which can be detected to a level of 10 nM with a linear range between 10(-8) and 10(-4) M.
Protonation Effects on Superexchange across Gold/Osmium Bis(bipyridyl) Tetrazine Chloride Monolayer Interfaces
Publisher: American Chemical Society (ACS)
Date: 16-03-2001
DOI: 10.1021/JP003984N
An unusually stable solid state Ag|AgCl reference electrode for long term continuous measurements based on a crosslinked poly(vinyl acetate)/KCl composite
Publisher: Elsevier BV
Date: 02-2021
Dynamics of Charge Transport through Osmium Tris Dimethoxy Bipyridyl Solid Deposits
Publisher: American Chemical Society (ACS)
Date: 17-05-2002
DOI: 10.1021/LA010927S
Effect of oxidant type on the chemiluminescence intensity from the reaction of tris(2,2′-bipyridyl)ruthenium(III) with various organic acids
Publisher: Elsevier BV
Date: 30-04-2007
DOI: 10.1016/J.TALANTA.2006.11.032
Abstract: An investigation into the chemiluminescence of fourteen organic acids and tris(2,2'-bipyridyl)ruthenium(II) was undertaken. Particular emphasis was placed upon the method of production of the reagent, tris(2,2'-bipyridyl)ruthenium(III), with cerium(IV) sulfate, potassium permanganate, lead dioxide and electrochemical generation. Analytically useful chemiluminescence was observed when Ce(IV) or potassium permanganate were employed as oxidants. The kinetics of analyte oxidation was related to the intensity of the chemiluminescence emission, which increased by three orders of magnitude for tartaric acid after 40h of oxidation.
Tuning the electrochemiluminescent properties of iridium complexes of N-heterocyclic carbene ligands
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8DT04433C
Abstract: A series of electrochemiluminescent iridium( iii ) N-heterocyclic carbene complexes have been prepared to tune electrochemical and spectroscopic behaviour.
Spatially-resolved multicolor bipolar electrochemiluminescence
Publisher: Elsevier BV
Date: 04-2017
Electrochemiluminescent Monomers for Solid Support Syntheses of Ru(II)-PNA Bioconjugates: Multimodal Biosensing Tools with Enhanced Duplex Stability
Publisher: American Chemical Society (ACS)
Date: 16-02-2012
DOI: 10.1021/IC202761W
Abstract: The feasibility of devising a solid support mediated approach to multimodal Ru(II)-peptide nucleic acid (PNA) oligomers is explored. Three Ru(II)-PNA-like monomers, [Ru(bpy)(2)(Cpp-L-PNA-OH)](2+) (M1), [Ru(phen)(2)(Cpp-L-PNA-OH)](2+) (M2), and [Ru(dppz)(2)(Cpp-L-PNA-OH)](2+) (M3) (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, dppz = dipyrido[3,2-a:2',3'-c]phenazine, Cpp-L-PNA-OH = [2-(N-9-fluorenylmethoxycarbonyl)aminoethyl]-N-[6-(2-(pyridin-2yl)pyrimidine-4-carboxamido)hexanoyl]-glycine), have been synthesized as building blocks for Ru(II)-PNA oligomers and characterized by IR and (1)H NMR spectroscopy, mass spectrometry, electrochemistry and elemental analysis. As a proof of principle, M1 was incorporated on the solid phase within the PNA sequences H-g-c-a-a-t-a-a-a-a-Lys-NH(2) (PNA1) and H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-lys-NH(2) (PNA4) to give PNA2 (H-g-c-a-a-t-a-a-a-a-M1-lys-NH(2)) and PNA3 (H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-M1-lys-NH(2)), respectively. The two Ru(II)-PNA oligomers, PNA2 and PNA3, displayed a metal to ligand charge transfer (MLCT) transition band centered around 445 nm and an emission maximum at about 680 nm following 450 nm excitation in aqueous solutions (10 mM PBS, pH 7.4). The absorption and emission response of the duplexes formed with the cDNA strand (DNA: 5'-T-T-T-T-T-T-T-A-T-T-G-C-T-T-T-3') showed no major variations, suggesting that the electronic properties of the Ru(II) complexes are largely unaffected by hybridization. The thermal stability of the PNA·DNA duplexes, as evaluated from UV melting experiments, is enhanced compared to the corresponding nonmetalated duplexes. The melting temperature (T(m)) was almost 8 °C higher for PNA2·DNA duplex, and 4 °C for PNA3·DNA duplex, with the stabilization attributed to the electrostatic interaction between the cationic residues (Ru(II) unit and positively charged lysine/arginine) and the polyanionic DNA backbone. In presence of tripropylamine (TPA) as co-reactant, PNA2, PNA3, PNA2·DNA and PNA3·DNA displayed strong electrochemiluminescence (ECL) signals even at submicromolar concentrations. Importantly, the combination of spectrochemical, thermal and ECL properties possessed by the Ru(II)-PNA sequences offer an elegant approach for the design of highly sensitive multimodal biosensing tools.
Electrochemiluminescence
Publisher: Springer International Publishing
Date: 2022
Fluoride-selective optical sensor based on the dipyrrolyl-tetrathiafulvalene chromophore.
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1OB06459B
Electrochemiluminescence of surface bound microparticles of ruthenium complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B918799P
Electrochemiluminescent Metallopolymer Coatings: Combined Light and Current Detection in Flow Injection Analysis
Publisher: American Chemical Society (ACS)
Date: 21-10-2000
DOI: 10.1021/AC000605D
Abstract: The application of thin films of the metallopolymer [Ru(bpy)2PVP10]2+ for the electrochemiluminescent (ECL) detection of oxalate in a flow injection analysis system is reported, where bpy is 2,2'-bipyridyl and PVP is poly(4-vinylpyridine). Immobilization of the ECL reagent means that it can be regenerated in situ, eliminating the need to constantly deliver it to the reaction zone. Electrochemically generated Ru3+ reacts with the analyte to form the excited-state [Ru2+]*, which luminesces at 610 nm. The reaction is optimal at low pH, where the layer is swollen and homogeneous charge transport through the layer is more facile. Unlike traditional approaches, we simultaneously monitor both the erometric and luminescent response of the modified electrode. The precision of both signals is similar at approximately 2% (n = 10). However, the ECL response has a larger dynamic range extending from the low-micromolar to high-millimolar range and a lower limit of detection, approximately 0.2 microM or 4 pmol of oxalate injected. The ECL approach displays excellent selectivity for oxalate over a wide range of potential interferences including oxygen, amines, iron sulfate, ammonium nitrate, urea, and glucose. Ascorbic acid represents the most significant ECL interference. However, the signal observed for a 1 mM solution of ascorbic acid is still only 2.6% of the response observed for the injection of a similar concentration of oxalate.
A conceptual framework for the development of iridium(iii ) complex-based electrogenerated chemiluminescence labels
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9SC01391A
Abstract: A new strategy to create iridium( iii )-based ECL labels reveals limitations of conventional approaches.
Front Cover: Electrochemically Sensitized Luminescence from Lanthanides in d‐/f‐Block Heteronuclear Arrays (ChemPhotoChem 1/2018)
Publisher: Wiley
Date: 2018
Electrochemically Sensitized Luminescence from Lanthanides in d‐/f‐Block Heteronuclear Arrays
Publisher: Wiley
Date: 2018
9-Vinylanthracene Based Fluorogens: Synthesis, Structure-Property Relationships and Applications
Publisher: MDPI AG
Date: 04-12-2017
Structural verification and new reactivity for Stang's reagent, [PhI(CN)][OTf]
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3DT01765F
Abstract: The solid-state structure of Stang's reagent is revealed, with confirmation of its existence as an ion-pair with triflate in solution. Further reactivity successfully delivers CN to pyridyl ligands.
A redox-mediator pathway for enhanced multi-colour electrochemiluminescence in aqueous solution
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1SC05609C
Abstract: A water-soluble Ir( iii ) complex is shown to enhance the ‘remote’ mechanism of the most widely used co-reactant ECL reaction of tris(2,2′-bipyridine)ruthenium( ii ) with tripropylamine.
Mobile phone-based electrochemiluminescence sensing exploiting the ‘USB On-The-Go’ protocol
Publisher: Elsevier BV
Date: 09-2015
Electrochemiluminescence energy transfer in mixed iridium-based redox copolymers immobilised as nanoparticles
Publisher: Elsevier BV
Date: 08-2019
Electrochemistry at Modified Interfaces: Foreword
Publisher: Elsevier BV
Date: 12-2017
A 1D Schiff base zinc polymer as a versatile metallo-ligand for the synthesis of polynuclear zinc cages
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2DT30715D
Abstract: The 1D polymeric Schiff base zinc complex, [LZn(2)Et(2)](n), where LH(2) = (NN'-ethylene-bis(4-iminopentan-2-one)) has been demonstrated as a useful synthetic metallo building block for the synthesis of homo and heteronuclear zinc cages. The reaction of [LZn(2)Et(2)](n) with CdI(2) afforded the hetero-nuclear cage, 1, [L(2)Zn(4)(Et)(2)CdI(4)], while reaction with HgI(2) afforded a hexanuclear zinc cage, [L(2)Zn(6)(Et)(4)(μ(4)O)(μ(3)OEt)I], 2. The versatility of [LZn(2)Et(2)](n) as a metallo building block is demonstrated through the reaction with ferrocenyl carboxylic acid, affording the ferrocenyl supported zinc cage, [L(2)Zn(8)(FcCO(2))(4)(Et)(2)(OEt)(2)(μ(4)O)(2)], 3, while the reaction with Er(III) acetate afforded the decanuclear zinc cage, [L(3)Zn(10)(μ(4)O)(4)(Et)(6)], 4.
A Strong cis-Effect in an Imidazole-Imidazolium-Substituted Alkene.
Publisher: Wiley
Date: 21-04-2017
Abstract: We report the first ex le of an alkene with two carbon-bound substituents (imidazole and imidazolium rings) where the Z-isomer has a greater thermodynamic stability than the E-isomer which persists in both the gas phase and in solution. Theoretical calculations, solution fluorescence spectroscopy and gas-phase ion mobility mass spectrometry studies confirm the preference for the Z-isomer, the stability of which is traced to a non-covalent interaction between the imidazole lone pair and the imidazolium ring.
Potential‐Resolved Electrogenerated Chemiluminescence for the Selective Detection of Multiple Luminophores
Publisher: Wiley
Date: 02-02-2015
Abstract: Electrogenerated chemiluminescence (ECL) is fundamentally dependent on the applied electrode potential, and measuring ECL intensity over a range of different potentials is commonly used to examine the underlying chemical reaction pathways responsible for the emission of light. Several research groups have now demonstrated that the applied potential can be exploited to selectively elicit ECL from: 1) multiple excited states within a single chemical species 2) multiple emitters sharing a common co-reactant or 3) distinct ECL systems. This new generation of multiplexed ECL processes has been facilitated by the extensive development of novel electrochemiluminophores and instrumental approaches such as the near-continuous collection of ECL spectra with CCD detectors during voltammetry or chrono erometry experiments.
Metallopolymers as Nanostructured Solid‐State Platforms for Electrochemiluminescence Applications
Publisher: Wiley
Date: 18-11-2019
Reagentless Electrochemiluminescence from a Nanoparticulate Polymer of Intrinsic Microporosity (PIM‐1) Immobilized onto Tin‐Doped Indium Oxide
Publisher: Wiley
Date: 21-09-2016
Control of Excitation and Quenching in Multi‐colour Electrogenerated Chemiluminescence Systems through Choice of Co‐reactant
Publisher: Wiley
Date: 09-09-2014
Abstract: We demonstrate a new approach to manipulate the selective emission in mixed electrogenerated chemiluminescence (ECL) systems, where subtle changes in co-reactant properties are exploited to control the relative electron-transfer processes of excitation and quenching. Two closely related tertiary-amine co-reactants, tri-n-propylamine and N,N-diisopropylethylamine, generate remarkably different emission profiles: one provides distinct green and red ECL from [Ir(ppy)3] (ppy=2-phenylpyridinato-C2,N) and a [Ru(bpy)3](2+) (bpy=2,2'-bipyridine) derivative at different applied potentials, whereas the other generates both emissions simultaneously across a wide potential range. These phenomena can be rationalized through the relative exergonicities of electron-transfer quenching of the excited states, in conjunction with the change in concentration of the quenchers over the applied potential range.
The final fate of NHC stabilized dicarbon
Publisher: Walter de Gruyter GmbH
Date: 14-02-2017
Abstract: In this paper we report the outcome of the reduction of NHC stabilized acetylenic dications, [NHC-C n -NHC] 2+ for n=2 and 4. The target compounds were NHC stabilized di- and tetracarbon in the form of NHC-C n -NHC. However, upon chemical reduction, decomposition ensues with release of the free NHC. This effect is also observed in electrochemical studies. This lends credence to Bestman’s hypothesis that two donor ligands cannot stabilize C n for n=even numbers.
Electrochemiluminescence of cyclometalated iridium (III) complexes
Publisher: Elsevier BV
Date: 2018
Erratum to Electrochemiluminescence of cyclometalated iridium (III) complexes (Current Opinion in Electrochemistry (2018) 8 (52–59) (S2451910317301461) (10.1016/j.coelec.2017.12.004))
Publisher: Elsevier BV
Date: 03-2018
Synthesis and electrochemical studies on a crown ether bearing a naphthoquinone acceptor
Publisher: CSIRO Publishing
Date: 2001
DOI: 10.1071/CH02030
Mediated Electron Transfer between FeII Adsorbed onto Hydrous Ferric Oxide and a Working Electrode
Publisher: American Chemical Society (ACS)
Date: 04-09-2014
DOI: 10.1021/ES501561D
Abstract: The redox properties of Fe(II) adsorbed onto mineral surfaces have been highly studied over recent years due to the wide range of environmental contaminants that react with this species via abiotic processes. In this work the reactivity of Fe(II) adsorbed onto hydrous ferric oxide (HFO) has been studied using ferrocene (bis-cyclopentadienyl iron(II) Fc) derivatives as electron shuttles in cyclic voltammetry (CV) experiments. The observed lification of the ferrocene oxidation peak in CV is attributed to reaction between the electrochemically generated ferrocenium (Fc(+)) ion and adsorbed Fe(II) species in a catalytic process (EC' mechanism). pH dependence studies show that the reaction rate increases with Fe(II) adsorption and is maintained in the absence of aqueous Fe(2+), providing strong evidence that the electron transfer process involves the adsorbed species. The rate of reaction between Fc(+) and adsorbed Fe(II) increases with the redox potential of the ferrocene derivative, as expected, with bimolecular rate constants in the range 10(3)-10(5) M(-1) s(-1). The ferrocene-mediated electrochemical method described has considerable promise in the development of a technique for measuring electron-transfer rates in geochemical and environmental systems.
A simple, low-cost instrument for electrochemiluminescence immunoassays based on a Raspberry Pi and screen-printed electrodes
Publisher: Elsevier BV
Date: 08-2022
DOI: 10.1016/J.BIOELECHEM.2022.108107
Abstract: A powerful, yet low-cost and semi-portable electrochemiluminescence (ECL) biosensing device is described. It is constructed around a Raspberry Pi single-board computer, which serves as the controller and user interface. The Pi is interfaced with an expansion board that controls the potential applied to a disposable screen-printed electrode and facilitates data acquisition from a photomultiplier tube (PMT), which detects the ECL emission from the sensor surface. As proof-of-concept, we demonstrate that this arrangement can quantitate tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)
Electrochemically tuneable multi-colour electrochemiluminescence using a single emitter
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6SC01912A
Abstract: A single component electrochemiluminescence system from which red, green, blue or white emission can be obtained, depending on the applied potential or the mode of the ECL experiment, is described.
Electrochemically, Spectrally, and Spatially Resolved Annihilation‐Electrogenerated Chemiluminescence of Mixed‐Metal Complexes at Working and Counter Electrodes
Publisher: Wiley
Date: 08-05-2018
Structural verification and new reactivity for Stang’s reagent, [PhI(CN)][OTf]
Publisher: American Chemical Society (ACS)
Date: 02-05-2023
DOI: 10.26434/CHEMRXIV-2023-ZLTXF
Abstract: The structure of Stang’s reagent [PhI(CN)][OTf] is confirmed by X-ray crystallography and is determined to be best described as an ion-pair in organic solution. It is found to be a strong Lewis acid, but reaction with pyridine ligands gives [Pyr-CN][OTf] salts via redox and represents the first path to a new derivative of the CDAP reagent widely used as an activation agent for polysaccharides.
Red–Green–Blue Electrogenerated Chemiluminescence Utilizing a Digital Camera as Detector
Publisher: American Chemical Society (ACS)
Date: 20-02-2014
DOI: 10.1021/AC404135F
Abstract: Exploiting the distinct excitation and emission properties of concomitant electrochemiluminophores in conjunction with the inherent color selectivity of a conventional digital camera, we create a new strategy for multiplexed electrogenerated chemiluminescence detection, suitable for the development of low-cost, portable clinical diagnostic devices. Red, green and blue emitters can be efficiently resolved over the three-dimensional space of ECL intensity versus applied potential and emission wavelength. As the relative contribution ratio of each emitter to the photographic RGB channels is constant, the RGB ECL intensity versus applied-potential curves could be effectively isolated to a single emitter at each potential.
Triamidetriamine Bearing Macrobicyclic and Macrotricyclic Ligands: Potential Applications in the Development of Copper-64 Radiopharmaceuticals
Publisher: American Chemical Society (ACS)
Date: 16-12-2013
DOI: 10.1021/IC4024508
Abstract: A versatile and straightforward synthetic approach is described for the preparation of triamide bearing analogues of sarcophagine hexaazamacrobicyclic cage ligands without the need for a templating metal ion. Reaction of 1,1,1-tris(aminoethyl)ethane (tame) with 3 equiv of 2-chloroacetyl chloride, yields the tris(α-chloroamide) synthetic intermediate 6, which when treated with either 1,1,1-tris(aminoethyl)ethane or 1,4,7-triazacyclononane furnished two novel triamidetriamine cryptand ligands (7 and 8 respectively). The Co(III) and Cu(II) complexes of cryptand 7 were prepared however, cryptand 8 could not be metalated. The cryptands and the Co(III) complex 9 have been characterized by elemental analysis, (1)H and (13)C NMR spectroscopy, and X-ray crystallography. These studies confirm that the Co(III) complex 9 adopts an octahedral geometry with three facial deprotonated amido-donors and three facial amine donor groups. The Cu(II) complex 10 was characterized by elemental analysis, single crystal X-ray crystallography, cyclic voltammetry, and UV-visible absorption spectroscopy. In contrast to the Co(III) complex (9), the Cu(II) center adopts a square planar coordination geometry, with two amine and two deprotonated amido donor groups. Compound 10 exhibited a quasi-reversible, one-electron oxidation, which is assigned to the Cu(2+/3+) redox couple. These cryptands represent interesting ligands for radiopharmaceutical applications, and 7 has been labeled with (64)Cu to give (64)Cu-10. This complex showed good stability when subjected to L-cysteine challenge whereas low levels of decomplexation were evident in the presence of L-histidine.
Nicotinamide-Appended Fluorophores as Fluorescent Redox Sensors
Publisher: CSIRO Publishing
Date: 2019
DOI: 10.1071/CH19398
Access to the Parent Tetrakis(pyridine)gold(III) Trication, Facile Formation of Rare Au(III) Terminal Hydroxides, and Preliminary Studies of Biological Properties
Publisher: American Chemical Society (ACS)
Date: 03-2016
DOI: 10.1021/ACS.INORGCHEM.5B02667
Abstract: In this paper we report on the use of [NO][BF4] to access tricationic tetrakis(pyridine)gold(III) from Au powder, a species inaccessible using the more traditional (tetrahydrothiophene)AuCl route. It is then demonstrated that this family of compounds can be used to access new terminal Au(III) hydroxides, a challenging class of compounds, and the first crystallographically characterized ex les employing bidentate ligands. Finally, preliminary biological studies indicate good activity for derivatives featuring polydentate ligands against the HeLa and PC3 cell lines but also strong inhibition of primary HUVEC cells.
Luminescent iridium(iii ) complexes of N-heterocyclic carbene ligands prepared using the ‘click reaction’
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9DT01362H
Abstract: Luminescent and electrochemiluminescent N-heterocyclic carbene-combined 1,2,3-triazole and 1,2,3-triazolylidene Ir( iii ) complexes have been prepared and their potential as luminescent probes in cell imaging has been evaluated.
Aggregation-Induced Electrochemiluminescence of Platinum(II) Complexes
Publisher: American Chemical Society (ACS)
Date: 03-10-2017
DOI: 10.1021/JACS.7B07710
Abstract: We report the electrochemiluminescence properties of square-planar Pt(II) complexes that result from the formation of supramolecular nanostructures. We define this new phenomenon as aggregation-induced electrochemiluminescence (AIECL). In this system, self-assembly changes the HOMO and LUMO energies, making their population accessible via ECL pathways and leading to the generation of the luminescent excited state. Significantly, the emission from the self-assembled system is the first ex le of electrochemiluminescence (ECL) of Pt(II) complexes in aqueous solution having higher efficiency than the standard, Ru(bpy)
A Family of Heterocyclic Naphthalene Diimide (NDI) Analogues: Comparing Parent Isoquinoline Diimides and Phthalazine Diimides with NDI
Publisher: Wiley
Date: 10-2019
Abstract: Parent isoquinoline diimide (IQDI) and phthalazine diimide (PTDI), as two new heterocyclic analogues of naphthalene diimides (NDIs), have been synthesized through an oxidative strategy in 35-79 % yield. X-ray crystallography has been used to support the formation of IQDI, which also show fluorescence quantum yields of 3.5 %. The electrochemical and electrical properties of these molecules have been studied. The electrochemical results show an interesting trend in first reduction potential PTDI<IQDI<NDI and 0.1 eV changes in the optical band gap (E
Near‐Infrared Electrochemiluminescence from Bistridentate Ruthenium(II) Di(quinoline‐8‐yl)pyridine Complexes in Aqueous Media
Publisher: Wiley
Date: 02-2020
A potential-controlled switch on/off mechanism for selective excitation in mixed electrochemiluminescent systems
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2SC21707D
Comparison of homoleptic and heteroleptic 2,2′-bipyridine and 1,10-phenanthroline ruthenium complexes as chemiluminescence and electrochemiluminescence reagents in aqueous solution
Publisher: Elsevier BV
Date: 03-2009
DOI: 10.1016/J.ACA.2008.12.042
Abstract: We have conducted a comprehensive comparative study of Ru(bipy)(3)(2+), Ru(bipy)(2)(phen)(2+), Ru(bipy)(phen)(2)(2+), and Ru(phen)(3)(2+) as chemiluminescence and electrochemiluminescence (ECL) reagents, to address several previous conflicting observations and gain a greater insight into their potential for chemical analysis. Clear trends were observed in many of their spectroscopic and electrochemical properties, but the relative chemiluminescence or ECL intensity with a range of analytes/co-reactants is complicated by the contribution of numerous (sometimes opposing) factors. Significantly, the reversibility of cyclic voltammetric responses for the complexes decreased as the number of phenanthroline ligands was increased, due to the lower stability of their ruthenium(III) form in the aqueous solvent. This trend was also evident over a longer timescale when the ruthenium(III) form was spectrophotometrically monitored after chemical oxidation of the ruthenium(II) complexes. In general, the greater stability of Ru(bipy)(3)(3+) resulted in lower blank signals, although this effect was less pronounced with ECL, where the reagent is oxidised in the presence of the co-reactants. Nevertheless, this shows the need to compare signal-to-blank ratios or detection limits, rather than the more common comparisons of overall signal intensity for different ruthenium complexes. Furthermore, our results support previous observations that, compared to Ru(bipy)(3)(2+), Ru(phen)(3)(2+) provides greater ECL and chemiluminescence intensities with oxalate, which in some circumstances translates to superior detection limits, but they do not support the subsequent generalised notion that Ru(phen)(3)(2+) is a more sensitive reagent than Ru(bipy)(3)(2+) for all analytes.
Electrogenerated Chemiluminescence Detection in Paper-Based Microfluidic Sensors
Publisher: American Chemical Society (ACS)
Date: 19-01-2011
DOI: 10.1021/AC102392T
Abstract: This paper describes the first approach at combining paper microfluidics with electrochemiluminescent (ECL) detection. Inkjet printing is used to produce paper microfluidic substrates which are combined with screen-printed electrodes (SPEs) to create simple, cheap, disposable sensors which can be read without a traditional photodetector. The sensing mechanism is based on the orange luminescence due to the ECL reaction of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) with certain analytes. Using a conventional photodetector, 2-(dibutylamino)ethanol (DBAE) and nicotinamide adenine dinucleotide (NADH) could be detected to levels of 0.9 μM and 72 μM, respectively. Significantly, a mobile camera phone can also be used to detect the luminescence from the sensors. By analyzing the red pixel intensity in digital images of the ECL emission, a calibration curve was constructed demonstrating that DBAE could be detected to levels of 250 μM using the phone.
Mediated electron transfer for electroanalysis: transport and kinetics in tin films of [Ru (bpy) 2 PVP 10 ] (ClO 4 ) 2
Publisher: Elsevier BV
Date: 09-1999
Probing Conformational Variation in Luminescent Dinuclear Gold(I) N‐Heterocyclic Carbene Complexes
Publisher: Wiley
Date: 16-08-2017
Unusually Strong Electrochemiluminescence from Iridium-Based Redox Polymers Immobilized As Thin Layers or Polymer Nanoparticles
Publisher: American Chemical Society (ACS)
Date: 02-10-2018
Abstract: A new class of redox metallopolymer based on cyclometalated iridium(III) centers is described, with unusually intense luminescence properties in aqueous media. We report the facile synthesis, photophysical and electrochemical characterization, supported by DFT calculations and their electrochemiluminescence (ECL) properties which, under some circumstances, are significantly greater than the analogous ruthenium-based materials. The photoluminescence (PL) and ECL of these materials are further dramatically enhanced when dispersed or immobilized as polymeric nanoparticles (PNPs). This aggregation-induced emission (AIE and AIECL) operates by providing important protection for the cyclometalated iridium(III) centers against the types of quenching processes which commonly afflict iridium-based luminophores in aqueous media. The results suggest interesting new avenues of research for the application of such materials in and PL and ECL-based detection and imaging as well as light-emitting devices.
Chemiluminescence and electrochemiluminescence detection of controlled drugs
Publisher: Wiley
Date: 10-12-2010
DOI: 10.1002/DTA.236
Abstract: We review the determination of various controlled drugs (opioids, tranquilizers, stimulants, and hallucinogens) using flow-analysis methodologies (flow injection analysis, high performance liquid chromatography, capillary electrophoresis, and microfluidic devices) with chemiluminescence and electrochemiluminescence reagents such as luminol, diaryloxalates, tris(2,2'-bipyridine)ruthenium(II), permanganate, manganese(IV), and sulfite, for industrial, clinical, pharmaceutical, and forensic science applications.
Electrochemiluminescent Peptide Nucleic Acid-Like Monomers Containing Ru(II)–Dipyridoquinoxaline and Ru(II)–Dipyridophenazine Complexes
Publisher: American Chemical Society (ACS)
Date: 31-10-2011
DOI: 10.1021/IC201911F
Abstract: A series of Ru(II)-peptide nucleic acid (PNA)-like monomers, [Ru(bpy)(2)(dpq-L-PNA-OH)](2+) (M1), [Ru(phen)(2)(dpq-L-PNA-OH)](2+) (M2), [Ru(bpy)(2)(dppz-L-PNA-OH)](2+) (M3), and [Ru(phen)(2)(dppz-L-PNA-OH)](2+) (M4) (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, dpq-L-PNA-OH = 2-(N-(2-(((9H-fluoren-9-yl)methoxy)carbonylamino)ethyl)-6-(dipyrido[3,2-a:2',3'-c]phenazine-11-carboxamido)hexanamido)acetic acid, dppz-L-PNA-OH = 2-(N-(2-(((9H-fluoren-9-yl) methoxy)carbonylamino)ethyl)-6-(dipyrido[3,2-f:2',3'-h]quinoxaline-2-carboxamido)acetic acid) have been synthesized and characterized by IR and (1)H NMR spectroscopy, mass spectrometry, and elemental analysis. As is typical for Ru(II)-tris(diimine) complexes, acetonitrile solutions of these complexes (M1-M4) show MLCT transitions in the 443-455 nm region and emission maxima at 618, 613, 658, and 660 nm, respectively, upon photoexcitation at 450 nm. Changes in the ligand environment around the Ru(II) center are reflected in the luminescence and electrochemical response obtained from these monomers. The emission intensity and quantum yield for M1 and M2 were found to be higher than for M3 and M4. Electrochemical studies in acetonitrile show the Ru(II)-PNA monomers to undergo a one-electron redox process associated with Ru(II) to Ru(III) oxidation. A positive shift was observed in the reversible redox potentials for M1-M4 (962, 951, 936, and 938 mV, respectively, vs Fc(0/+) (Fc = ferrocene)) in comparison with [Ru(bpy)(3)](2+) (888 mV vs Fc(0/+)). The ability of the Ru(II)-PNA monomers to generate electrochemiluminescence (ECL) was assessed in acetonitrile solutions containing tripropylamine (TPA) as a coreactant. Intense ECL signals were observed with emission maxima for M1-M4 at 622, 616, 673, and 675 nm, respectively. At an applied potential sufficiently positive to oxidize the ruthenium center, the integrated intensity for ECL from the PNA monomers was found to vary in the order M1 (62%) > M3 (60%) > M4 (46%) > M2 (44%) with respect to [Ru(bpy)(3)](2+) (100%). These findings indicate that such Ru(II)-PNA bioconjugates could be investigated as multimodal labels for biosensing applications.
New perspectives on the annihilation electrogenerated chemiluminescence of mixed metal complexes in solution
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6SC01570K
Abstract: We examine energy transfer and quenching within annihilation ECL systems comprising mixed metal-complexes in solution, and show the dependence of the emission intensities on luminophore concentration and the applied potentials.
A study of [Os(bipy)2(PVP)3.3(PS)6.7Cl]+ polymer film modified electrodes using neutron reflectivity
Publisher: Royal Society of Chemistry (RSC)
Date: 1999
DOI: 10.1039/A808393B
Considering the chemical energy requirements of the tri-n-propylamine co-reactant pathways for the judicious design of new electrogenerated chemiluminescence detection systems
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5AN01462J
Abstract: A simple graphical approach to characterise the energetically feasible electrogenerated chemiluminescence (ECL) reaction pathways with tri- n -propylamine is discussed.
A simple strategy for enhancing the detection limits of blue-green ECL emitters
Publisher: Elsevier BV
Date: 09-2023
Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2′-bipyridine)ruthenium(ii) complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0AN00952K
Abstract: Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For ex le, the same factors that determine ΔG for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (Φ(ex)) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (Φ(p)) and the possibility of competing side reactions are found to be the main determinants of ECL intensity.
Chapter 8. Multicolour Electrochemiluminescence
Publisher: Royal Society of Chemistry
Date: 2019
Electrogenerated chemiluminescence of tris(2,2′ bipyridine)ruthenium(ii ) using common biological buffers as co-reactant, pH buffer and supporting electrolyte
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5AN01216C
Abstract: A series of aliphatic tertiary amines commonly used to buffer the pH in biological experiments, were examined as alternative, non-toxic co-reactants for electrogenerated chemiluminescence.
Wide Bite Angle Disphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications
Publisher: American Chemical Society (ACS)
Date: 18-02-2021
DOI: 10.26434/CHEMRXIV.14046449
Abstract: We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu (P^P) (dmphen)]BF sub /sub , where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid-state, with Φ sub PL /sub of up to 35%, and in solution, with Φ sub PL /sub of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the %V sub bur /sub of the P^P ligand. The most emissive complexes were used to fabricate both organic light-emitting diodes (OLEDs) and light-emitting electrochemical calls (LECs), both of which showed moderate performance. Compared to the benchmark Cu(I)-based LECs, [Cu(dnbp)(DPEPhos)] sup + /sup (EQE sub max /sub = 16%), complex b /b (EQE sub max /sub = 1.85%) showed much longer device lifetime (t sub /2 /sub = 1.25 h and .5 h for [Cu(dnbp)(DPEPhos)] sup + /sup and complex b /b , respectively). The electrochemiluminescent properties of several complexes were also studied which to the best of our knowledge constitutes the first ECL study for heteroleptic copper (I) complexes. Notably, complexes exhibiting more reversible electrochemistry were associated with higher annihilation ECL as well as better performance in an LEC device.
Labeling phospholipid membranes with lipid mimetic luminescent metal complexes
Publisher: Elsevier BV
Date: 11-2014
DOI: 10.1016/J.BBAMEM.2014.08.005
Abstract: Lipid-mimetic metallosurfactant based luminophores are promising candidates for labeling phospholipid membranes without altering their biophysical characteristics. The metallosurfactants studied exhibit high structural and physicochemical similarity to phospholipid molecules, designed to incorporate into the membrane structure without the need for covalent attachment to a lipid molecule. In this work, two lipid-mimetic phosphorescent metal complexes are described: [Ru(bpy)2(dn-bpy)](2+) and [Ir(ppy)2(dn-bpy)](+) where bpy is 2,2'-bipyridine, dn-bpy is 4,4'-dinonyl-2,2'-bipyridine and ppy is 2-phenylpyridine. Apart from being lipid-mimetic in size, shape and physical properties, both complexes exhibit intense photoluminescence and enhanced photostability compared with conventional organic fluorophores, allowing for prolonged observation. Moreover, the large Stokes shift and long luminescence lifetime associated with these complexes make them more suitable for spectroscopic studies. The complexes are easily incorporated into dimyristoil-phosphatidyl-choline (DMPC) liposomes by mixing in the organic solvent phase. DLS reveals the labeled membranes form liposomes of similar size to that of neat DMPC membrane. Synchrotron Small-Angle X-ray Scattering (SAXS) measurements confirmed that up to 5% of either complex could be incorporated into DMPC membranes without producing any structural changes in the membrane. Fluorescence microscopy reveals that 0.5% label content is sufficient for imaging. Atomic Force Microscopic imaging confirms that liposomes of the labeled bilayers on a mica surface can fuse into a flat lamellar membrane that is morphologically identical to neat lipid membranes. These results demonstrate the potential of such lipid-mimetic luminescent metal complexes as a new class of labels for imaging lipid membranes.
Electrochemiluminescence Amplification in Bead-Based Assays Induced by a Freely Diffusing Iridium(III) Complex
Publisher: American Chemical Society (ACS)
Date: 26-01-2023
The Fate of NHC‐Stabilized Dicarbon
Publisher: Wiley
Date: 14-01-2015
Abstract: The attempted synthesis of NHC-stabilized dicarbon (NHC=C=C=NHC) through deprotonation of a doubly protonated precursor ([NHC-CH=CH-NHC](2+) ) is reported. Rather than deprotonation, a clean reduction to NHC=CH-CH=NHC is observed with a variety of bases. The apparent resistance towards deprotonation to the target compound led to a reinvestigation of the electronic structure of NHC→CC←NHC, which showed that the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) gap is likely too small to allow for isolation of this species. This is in contrast to the recent isolation of the cyclic alkylaminocarbene analogue (cAAC=C=C=cAAC), which has a large HOMO-LUMO gap. A detailed theoretical study illuminates the differences in electronic structures between these molecules, highlighting another case of the potential advantages of using cAAC rather than NHC as a ligand. The bonding analysis suggests that the dicarbon compounds are well represented in terms of donor-acceptor interactions L→C2 ←L (L=NHC, cAAC).
Facile Analysis of EC Cyclic Voltammograms
Publisher: American Chemical Society (ACS)
Date: 11-03-2004
DOI: 10.1021/AC035108M
Abstract: It has been found empirically that, for an E(rev)C(irrev) process, the forward/backward ratio of the peak height magnitudes in cyclic voltammetry equals 1 + ktau, where k is the rate constant of the chemical reaction and tau is the time required for the scan to travel between the half-wave and reversal potentials. The relationship is largely independent of the scan rate and the reversal potential, except insofar as these influence tau. Though not exact, the relationship is obeyed closely enough to provide accurate rate constants under favorable conditions. The utility of this simple formula in extracting homogeneous kinetic information is demonstrated using experimental data for the electron-transfer-induced isomerization of an octahedral manganese complex. An explanation of the relationship is presented, as is a more exact formula that reduces to 1 + ktau when k is small. A semiquantitative explanation of the relationship is provided.
A 24-Crown-8 Bearing Naphthalene and Naphthoquinone Chromophores
Publisher: Informa UK Limited
Date: 10-2005
Facile Formation of Homoleptic Au(III) Trications via Simultaneous Oxidation and Ligand Delivery from [PhI(pyridine)2]2+
Publisher: American Chemical Society (ACS)
Date: 21-08-2014
DOI: 10.1021/JA506365M
Abstract: We report the first ex les of Au(III) tricationic complexes bound only by neutral monodentate ligands, which are a new class of gold reagents. Oxidative addition to the bis-pyridine Au(I) cation, [Au(4-DMAP)2](+), using a series of dicationic I(III) oxidants of the general form [PhI(L)2](2+) (L = pyridine, 4-DMAP, 4-cyanopyridine) allows ready access to homoleptic and pseudo-homoleptic Au(III) complexes [Au(4-DMAP)2(L)2](3+). The facile oxidative addition of Au(I) species additionally demonstrates the efficacy of PhI(L)2](2+) reagents as halide-free oxidants for Au(I). Comparisons are made via attempts to oxidize NHC-Au(I)Cl, where introduction of the chloride anion results in complex mixtures via ligand and chloride exchange, demonstrating the advantage of using the pyridine-based homoleptic compounds. The new Au(III) trications show intriguing reactivity with water, yielding dinuclear oxo-bridged and rare terminal Au(III)-OH complexes.
Luminescent iridium(iii)–boronic acid complexes for carbohydrate sensing
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0DT02177F
Abstract: A family of four Ir( iii ) complexes with either pyridyl-1,2,4-triazole or pyridyl-1,3,4-oxadiazole ligands bearing boronic acid groups have been prepared as potential luminescent sensors for carbohydrates.
Construction of a Highly Sensitive Thiol‐Reactive AIEgen‐Peptide Conjugate for Monitoring Protein Unfolding and Aggregation in Cells
Publisher: Wiley
Date: 24-10-2021
Abstract: Impairment of the protein quality control network leads to the accumulation of unfolded and aggregated proteins. Direct detection of unfolded protein accumulation in the cells may provide the possibility for early diagnosis of neurodegenerative diseases. Here a new platform based on a peptide‐conjugated thiol‐reactive aggregation‐induced emission fluorogen (AIEgen), named MI‐BTD‐P (or D1), for labeling and tracking unfolded proteins in cells is reported. In vitro experiments with model proteins show that the non‐fluorescent D1 only becomes highly fluorescent when reacted with the thiol group of free cysteine (Cys) residues on unfolded proteins but not glutathione or folded proteins with buried or surface exposed Cys. When the labeled unfolded proteins form aggregates, D1 fluorescence intensity is further increased, and fluorescence lifetime is prolonged. D1 is then used to measure unfolded protein loads in cells by flow cytometry and track the aggregate formation of the D1 labeled unfolded proteins using confocal microscopy. In combination with fluorescence lifetime imaging technique, the proteome at different folding statuses can be better differentiated, demonstrating the versatility of this new platform. The rational design of D1 demonstrates the outlook of incorporation of erse functional groups to achieve maximal sensitivity and selectivity in biological s les.
Phase, Morphology, and Particle Size Changes Associated with the Solid−Solid Electrochemical Interconversion of TCNQ and Semiconducting CuTCNQ (TCNQ = Tetracyanoquinodimethane)
Publisher: American Chemical Society (ACS)
Date: 21-08-2003
DOI: 10.1021/CM0341336
Solid state spectroelectrochemistry of microparticles of ruthenium diimine complexes immobilised on optically transparent electrodes
Publisher: Springer Science and Business Media LLC
Date: 17-12-2008
Facile Tuning of Luminescent Platinum(II) Schiff Base Complexes from Yellow to Near‐Infrared: Photophysics, Electrochemistry, Electrochemiluminescence and Theoretical Calculations
Publisher: Wiley
Date: 02-10-2013
Abstract: The photophysical and related properties of platinum(II) Schiff base complexes can be finely and predictably tuned over a wide range of wavelengths by small and easily implemented changes to ligand structure. A series of such complexes, differing only in the number and positioning of methoxy substituents on the phenoxy ring, were synthesised and their photophysical, electrochemical and electrochemiluminescent (ECL) properties investigated. Theoretical calculations were performed in order to gain further insight into the relationship between structure and properties in these materials. By positioning methoxy groups para and/or ortho to either the imine or the oxygen group on the ligand, electron density could be directed selectively toward the LUMO or HOMO as required. This allowed the emission colour (both photoluminescent and electrochemiluminescent) to be tuned over a wide range between 587 and 739 nm. The variation in orbital energies was also manifested in the positions of the absorption bands and the redox properties of the complexes, as well as in the NMR shifts for the uncoordinated ligands. All reported complexes displayed intense electrochemiluminescence (ECL), which could be initiated either by annihilation or co-reactant pathways. The relationship between the electrochemical and photophysical properties and the efficiency of the ECL is discussed. For two of the complexes solid-state ECL could be generated from electrodeposited layers of the complex.
Reprint of: Use of a mobile phone for potentiostatic control with low cost paper-based microfluidic sensors
Publisher: Elsevier BV
Date: 11-2013
DOI: 10.1016/J.ACA.2013.08.014
Abstract: By exploiting its ability to play sounds, a mobile phone with suitable software installed can serve the basic functions of a potentiostat in controlling an applied potential to oxidise ECL-active molecules, while the resultant photonic signal is monitored using the camera in video mode. In combination with paper microfluidic sensors this opens significant new possibilities for low-cost, instrument-free sensing.
Iridium(iii ) N-heterocyclic carbene complexes: an experimental and theoretical study of structural, spectroscopic, electrochemical and electrogenerated chemiluminescence properties
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4DT03378G
Abstract: Theoretical and experimental studies of a series of iridium N-heterocyclic carbene complexes.
Understanding Electrogenerated Chemiluminescence Efficiency in Blue-Shifted Iridium(III)-Complexes: An Experimental and Theoretical Study
Publisher: Wiley
Date: 03-03-2014
Abstract: Compared to tris(2-phenylpyridine)iridium(III) ([Ir(ppy)3 ]), iridium(III) complexes containing difluorophenylpyridine (df-ppy) and/or an ancillary triazolylpyridine ligand [3-phenyl-1,2,4-triazol-5-ylpyridinato (ptp) or 1-benzyl-1,2,3-triazol-4-ylpyridine (ptb)] exhibit considerable hypsochromic shifts (ca. 25-60 nm), due to the significant stabilising effect of these ligands on the HOMO energy, whilst having relatively little effect on the LUMO. Despite their lower photoluminescence quantum yields compared with [Ir(ppy)3 ] and [Ir(df-ppy)3 ], the iridium(III) complexes containing triazolylpyridine ligands gave greater electrogenerated chemiluminescence (ECL) intensities (using tri-n-propylamine (TPA) as a co-reactant), which can in part be ascribed to the more energetically favourable reactions of the oxidised complex (M(+) ) with both TPA and its neutral radical oxidation product. The calculated iridium(III) complex LUMO energies were shown to be a good predictor of the corresponding M(+) LUMO energies, and both HOMO and LUMO levels are related to ECL efficiency. The theoretical and experimental data together show that the best strategy for the design of efficient new blue-shifted electrochemiluminophores is to aim to stabilise the HOMO, while only moderately stabilising the LUMO, thereby increasing the energy gap but ensuring favourable thermodynamics and kinetics for the ECL reaction. Of the iridium(III) complexes examined, [Ir(df-ppy)2 (ptb)](+) was most attractive as a blue-emitter for ECL detection, featuring a large hypsochromic shift (λmax =454 and 484 nm), superior co-reactant ECL intensity than the archetypal homoleptic green and blue emitters: [Ir(ppy)3 ] and [Ir(df-ppy)3 ] (by over 16-fold and threefold, respectively), and greater solubility in polar solvents.
Solution and solid-state electrochemiluminescence of a fac-tris(2-phenylpyridyl)iridium(III)-cored dendrimer
Publisher: Elsevier BV
Date: 06-2013
Mixed annihilation electrogenerated chemiluminescence of iridium(iii ) complexes
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8CP01737A
Abstract: The annihilation electrogenerated chemiluminescence of mixtures of Ir( iii ) complexes is eliminated by manipulating reduction potentials through subtle changes in ligand structure.
A FRET-based ratiometric redox probe for detecting oxidative stress by confocal microscopy, FLIM and flow cytometry
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5CC03394B
Abstract: A FRET-based, ratiometric redox probe undergoes a fluorescence colour change upon reduction, and can be used to study cellular oxidative capacity using confocal microscopy, fluorescence lifetime imaging and flow cytometry.
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