Metal-to-ligand charge-transfer excited-states in binuclear copper(I) complexes. Tuning MLCT excited-states through structural modification of bridging ligands. A resonance Raman study

Waterland, Mark R.; Flood, Amar H.; Gordon, Keith C.

doi:10.1039/a909121a

Cited by 14 publications

(8 citation statements)

References 49 publications

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“…Resonance Raman spectra were recorded using a setup described previously. − Briefly, a continuous-wave krypton-ion laser (Innova I-302, Coherent, Inc.), solid-state 444 nm diode (Crystal Laser), solid-state 532 nm Nd:YAG (B&W Tec Inc.), helium−neon (Oplectra, Germany), or argon-ion laser (Melles Griot Omnichrome MAP-543) was used to generate resonance Raman scattering. Band-pass filters removed the ion plasma emission lines from the laser output.…”

Section: Methodsmentioning

confidence: 99%

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

et al. 2010

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Officer, D. L. (2010). Indanedione-substituted poly(terthiophene)s: Processable conducting polymers with intramolecular charge transfer interactions. Macromolecules, 43 (8), 3817-3827. Indanedione-substituted poly(terthiophene)s: Processable conducting polymers with intramolecular charge transfer interactions AbstractThe electrochemical and chemical syntheses of poly(terthiophene)s bearing an indanedione pendant group and displaying intramolecular charge transfer interactions have been achieved. The nature of the charge transfer interaction is characterized through DFT calculations and experimental studies, including resonance Raman spectroscopy and absorption and emission data through a Lippert-Mataga analysis. It is found that the low-energy transition present in the indanedione-bearing monomer species has considerable charge transfer character with a dipole change of II D. Decomposition of the indanedione group occurred during hydrazine reduction after chemical polymerization. A soluble, low molecular weight indanedione-substituted polymer (weight average 4500 Da) was nonetheless obtained following the use of a milder reducing agent, triethanolamine. To the best of our knowledge, this is the first example of the use of triethanolamine for the reduction of an oxidized polythiophene, providing a milder and safer alternative to hydrazine. In an attempt to produce higher molecular weight processable polymers with intramolecular charge transfer interactions, a copolymer of the indanedione-substituted terthiophene and a dihexylterthiophene was synthesized. The electronic conjugation of the produced polymers was characterized by Raman frequency dispersion experiments and show dispersion rate parameters similar to those observed for other substituted polythiophenes. ABSTRACT: The electrochemical and chemical syntheses of poly(terthiophene)s bearing an indanedione pendant group and displaying intramolecular charge transfer interactions have been achieved. The nature of the charge transfer interaction is characterized through DFT calculations and experimental studies, including resonance Raman spectroscopy and absorption and emission data through a Lippert-Mataga analysis. It is found that the low-energy transition present in the indanedione-bearing monomer species has considerable charge transfer character with a dipole change of 11 D. Decomposition of the indanedione group occurred during hydrazine reduction after chemical polymerization. A soluble, low molecular weight indanedionesubstituted polymer (weight average 4500 Da) was nonetheless obtained following the use of a milder reducing agent, triethanolamine. To the best of our knowledge, this is the first example of the use of triethanolamine for the reduction of an oxidized polythiophene, providing a milder and safer alternative to hydrazine. In an attempt to produce higher molecular weight processable polymers with intramolecular charge transfer interactions, a copolymer of the indanedione-substituted terthiophene and a dihexylterthiophene was synthesized. The ...

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Section: Methodsmentioning

confidence: 99%

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

et al. 2010

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“…Transition-metal complexes have attracted significant attention because of their intriguing architectures, topologies, and optoelectronic (OE) properties. − In these complexes, the redox-active metal centers are responsible for different shapes, sizes, and geometries, while the organic part tunes and controls the photophysical and physicochemical properties. , Furthermore, interaction between metal and conjugated organic spacers imparts low-energy electronic transition to the molecules . Among different transition metals, the monovalent copper (Cu(I)) ion has emerged as a potential candidate for the development of a new generation of hybrid materials.…”

Section: Introductionmentioning

confidence: 99%

Dicopper(I) Complexes Incorporating Acetylide-Functionalized Pyridinyl-Based Ligands: Synthesis, Structural, and Photovoltaic Studies

et al. 2018

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Heteroaryl incorporated acetylide-functionalized pyridinyl ligands (L1-L6) with the general formula Py-C≡C-Ar (Py = pyridine and Ar = thiophene-2-yl, 2,2' -bithiophene]-5-yl, 2,2' :5',2″ -terthiophene]-5-yl, thieno[2,3- b]thiophen-2-yl, quinoline-5-yl, benzo[c][1,2,5]thiadiazole-5-yl) have been synthesized by Pd(0)/Cu(I)-catalyzed cross-coupling reaction of 4-ethynylpyridine and the respective heteroaryl halide. Ligands L1-L6 were isolated in respectable yields and characterized by microanalysis, IR spectroscopy, H NMR spectroscopy, and ESI-MS mass spectrometry. A series of dinuclear Cu(I) complexes 1-10 have been synthesized by reacting L1-L6 with CuI and triphenylphosphine (PPh) (R1) or with an anchored phosphine derivative, 4-(diphenylphosphino) benzoic acid (R2)/2-(diphenylphosphino)benzenesulfonic acid (R3), in a stoichiometric ratio. The complexes are soluble in common organic solvents and have been characterized by analytical, spectroscopic, and computational methods. Single-crystal X-ray structure analysis confirmed rhomboid dimeric structures for complexes 1, 2, 4, and 5, and a polymeric structure for 6. Complexes 1-6 showed oxidation potential responses close to 0.9 V vs Fc, which were chemically irreversible and are likely to be associated with multiple steps and core oxidation. Preliminary photovoltaic (PV) results of these new materials indicated moderate power conversion efficiency (PCE) in the range of 0.15-1.56% in dye-sensitized solar cells (DSSCs). The highest PCE was achieved with complex 10 bearing the sulfonic acid anchoring functionality.

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“…In addition to the exciplex-model discussed above (Section 4.3) the THEXI-states of complexes based on [Cu(dmp) 2 ] + have also been examined, using transient and time-resolved resonance Raman techniques [12,[131][132][133]. Like [Ru(bpy) 3 ] 2+ derivatives, synthesis of these compounds is reasonably straightforward and they exhibit interesting photophysical properties.…”

Section: Time-resolved Methods-direct Observation Of the Excited Statementioning

confidence: 99%

Understanding excited-state structure in metal polypyridyl complexes using resonance Raman excitation profiles, time-resolved resonance Raman spectroscopy and density functional theory

Horvath

Gordon

2010

Coordination Chemistry Reviews

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Metal-to-ligand charge-transfer excited-states in binuclear copper(I) complexes. Tuning MLCT excited-states through structural modification of bridging ligands. A resonance Raman study

Cited by 14 publications

References 49 publications

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

Indanedione-Substituted Poly(terthiophene)s: Processable Conducting Polymers with Intramolecular Charge Transfer Interactions

Dicopper(I) Complexes Incorporating Acetylide-Functionalized Pyridinyl-Based Ligands: Synthesis, Structural, and Photovoltaic Studies

Understanding excited-state structure in metal polypyridyl complexes using resonance Raman excitation profiles, time-resolved resonance Raman spectroscopy and density functional theory

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