Photoexcitation in Cu(I) and Re(I) Complexes Containing Substituted Dipyrido[3,2-<i>a</i>:2‘,3‘-<i>c</i>]phenazine:  A Spectroscopic and Density Functional Theoretical Study

Walsh, Penny J.; Gordon, Keith C.; Lundin, Natasha J.; Blackman, Allan G.

doi:10.1021/jp051009w

Cited by 66 publications

(67 citation statements)

References 49 publications

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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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“…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%

“…The resulting mean absolute deviations (MADs) of the frequencies are shown in Table 4; the values are indicative of satisfactory calculations. [29,[43][44][45][47][48][49][50][51] …”

Section: Synthesis and Characterisation Of Polyphosphazenesmentioning

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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“…The output frequencies were scaled by a factor of approximately 0.975 to minimize mean actual deviation (MAD) between the experimental and the calculated spectra [52].…”

Section: Computational Calculationsmentioning

confidence: 99%

Luminescent sensor for copper(II) ion based on imine functionalized monometallic rhenium(I) complexes

Ramdass¹,

Sathish²,

Velayudham

et al. 2017

Sensors and Actuators B: Chemical

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Photoexcitation in Cu(I) and Re(I) Complexes Containing Substituted Dipyrido[3,2-a:2‘,3‘-c]phenazine: A Spectroscopic and Density Functional Theoretical Study

Cited by 66 publications

References 49 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

Spectroscopic Studies of Phosphazene Polymers Containing Photoluminescent Metal Complexes

Luminescent sensor for copper(II) ion based on imine functionalized monometallic rhenium(I) complexes

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