Ultrafast dynamics in Cu(I)bisdiimine complexes from resonance Raman intensities

Lind, Samuel J.; Gordon, Keith C.; Waterland, Mark R.

doi:10.1002/jrs.2038

Cited by 46 publications

(46 citation statements)

References 60 publications

(37 reference statements)

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“…Resonance Raman spectra were recorded using a setup described previously. [34][35][36][37] Spectra from the ground state were generated via excitation with 413. Dye-sensitized solar cell fabrication and photoelectrochemical measurements were performed as described previously without modification.…”

Section: Methodsmentioning

confidence: 99%

A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes

Lind

Gordon

Gambhir

et al. 2009

Phys. Chem. Chem. Phys.

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Officer, D. L. (2009). A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes. Physical Chemistry Chemical Physics, 11 (27),[5598][5599][5600][5601][5602][5603][5604][5605][5606][5607] A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes Abstract A combination of density functional theory calculations, electronic absorption and resonance Raman spectroscopy has been applied to a series of beta-substituted zinc porphyrins to elucidate how the substituent affects the electronic structure of the metalloporphyrin and assign the nature of electronic transitions in the visible region. The use of conjugated beta substituents invokes a large perturbation to both the nature and energy of the frontier molecular orbitals and results in the generation of additional molecular orbitals from the parent metalloporphyrin species. A complicated electronic absorption spectra is observed which can be rationalised by an extension of Goutermans' four-orbital model. The excitations involved in the visible transitions have been determined using resonance Raman spectroscopy. This has revealed that the B band retains much of its original nature and is centred largely on the porphyrin core. Additional electronic transitions invoke population of orbitals localised on the substituent chain. The nature of the electronic transitions depends heavily on the type of b substituent. The results of this investigation question some previously held beliefs for the rational design of metalloporphyrins for dye-sensitized solar cell applications. A combination of density functional theory calculations, electronic absorption and resonance Raman spectroscopy has been applied to a series of b-substituted zinc porphyrins to elucidate how the substituent affects the electronic structure of the metalloporphyrin and assign the nature of electronic transitions in the visible region. The use of conjugated b substituents invokes a large perturbation to both the nature and energy of the frontier molecular orbitals and results in the generation of additional molecular orbitals from the parent metalloporphyrin species. A complicated electronic absorption spectra is observed which can be rationalised by an extension of Goutermans' four-orbital model. The excitations involved in the visible transitions have been determined using resonance Raman spectroscopy. This has revealed that the B band retains much of its original nature and is centred largely on the porphyrin core. Additional electronic transitions invoke population of orbitals localised on the substituent chain. The nature of the electronic transitions depends heavily on the type of b substituent. The results of this investigation question some previously held beliefs for the rational design of metalloporphyrins for dye-sensitized solar cell applications.

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Section: Methodsmentioning

confidence: 99%

A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes

Lind

Gordon

Gambhir

et al. 2009

Phys. Chem. Chem. Phys.

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“…These include: a study on polarization-sensitive CARS spectroscopy of free-base porphyrins; [1] a study on the ultrafast bimolecular radical reaction between S 1 p-terphenyl and carbon tetrachloride; [2] a time-resolved resonance Raman and density functional theory study of the deprotonation reaction of the triplet state of para-hydroxybenzophenone in mixed acetonitrile/water solutions; [3] an investigation of femtosecond Raman-induced Kerr effect spectroscopy; [4] a paper on ultrafast vibrational dynamics and solvation complexes of methyl acetate in methanol studied by sub-picosecond infrared spectroscopy; [5] an ultrafast dynamics and photochemistry study of π − π * excited trans-azobenzene; [6] a paper on ultrafast dynamics in Cu(I)bisdiimine complexes from resonance Raman intensities; [7] a three-state model for femtosecond broadband stimulated Raman scattering; [8] a picosecond time-resolved ultraviolet resonance Raman study on photoinduced electron transfer in glucose oxidase; [9] a study on molecular vibrational imaging of a human cell by multiplex coherent anti-Stokes Raman scattering microspectroscopy using a supercontinuum light source; [10] a paper on characteristic wavenumber shifts of the stimulated Raman scattering from interfacial water molecules induced by laser-induced plasma generation at air-water and water-silver interfaces; [11] a study on the identification of chemical species of fluorescein isothiocyanate isomer-I (FITC) monolayers on platinum by doubly resonant sum-frequency generation spectroscopy; [12] a work on coherent acoustic phonons in a thin gold film probed by femtosecond surface plasmon resonance; [13] a review of recent advances in linear and nonlinear Raman spectroscopy; [14] an investigation of the halide-ion-assisted increase of surfaceenhanced hyper-Raman scattering; [15] and finally a study on ultrafast Raman loss spectroscopy [16] . …”

mentioning

confidence: 99%

Editorial

Kiefer¹

2009

J Raman Spectroscopy

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“…Resonance Raman spectra were recorded in 10 -3 mol/L CH 2 Cl 2 solutions using a set-up previously described. [48,66] In short, the excitation beam and collection lens are in a 135°backscattering arrangement. Scattered photons were focused on the entrance slit of an Acton SpectraPro500i spectrograph with a 1200 grooves/mm grating, which disperses the radiation in a horizontal plane on a Princeton Instruments Spec10 liquid-nitrogen-cooled CCD detector.…”

Section: Methodsmentioning

confidence: 99%

Spectroscopic Studies of Phosphazene Polymers Containing Photoluminescent Metal Complexes

et al. 2011

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A series of small phosphazene ligands with pendant 6‐phenyl‐2,2′‐bipyridyl moieties, namely L1 [N3P3(OPh)5(OPhbpyPh)], L2 [N3P3(biph)2(OPhbpyPh)2], L3 [N3P3(tBubiph)2(OPhbpyPh)2], L4 [N3P3(biph)2(OPhbpyPh)Cl] and L5 [N3P3(biph)2(OPhbpyPh)(OPh)] [OPhbpyPh = 4‐(4‐phenoxy)‐6‐phenyl‐2,2′‐bipyridine, OPh = phenoxy, biph = 2,2′‐oxybiphenyl and tBubiph = 4,4′‐di‐tert‐butyl‐2,2′‐oxybiphenyl], have been used to synthesise the new cyclometallated palladium(II) and platinum(II) complexes [(L1‐H)PdCl], [(L1‐H)PtCl], [(L1‐H)(PdCl)2], [(L3‐H)(PdCl)2], [(L4‐H)PtCl], [(L5‐H)PtCl] and the rhenium(I) complex [L5Re(CO)3Cl]. Single‐crystal X‐ray diffraction analysis was performed on the free ligand L2 and the palladium complexes [(L1‐H)PdCl] and [(L3‐H)(PdCl)2]. In both PdII complexes, the metal centre lies in a distorted square‐planar geometry with an “N2CCl” donor set confirming the cyclopalladation. The ligand pendant arms are involved in intermolecular stacking interactions with adjacent molecules. A polyphosphazene (L6) with 4‐tert‐butylphenoxy (OtBuPh) and the potential donor OPhbpyPh as pendant groups was prepared and used to synthesise metallopolymers with ReI and PtII. Spectroscopic and computational studies were conducted to compare the discrete complexes with the polymers with similar metal pendants as well as to model compounds in the literature. By using UV/Vis and resonance Raman spectroscopic techniques it was found that very few deviations from known metal chromophores exist for both the triphosphazene‐ and polyphosphazene‐based complexes. The transient resonance Raman spectra of the PtII complexes revealed a ligand radical anion signature associated with the N2C unit.

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Ultrafast dynamics in Cu(I)bisdiimine complexes from resonance Raman intensities

Cited by 46 publications

References 60 publications

A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes

A spectroscopic and DFT study of thiophene-substituted metalloporphyrins as dye-sensitized solar cell dyes

Editorial

Spectroscopic Studies of Phosphazene Polymers Containing Photoluminescent Metal Complexes

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