Structure and reactivity of the metal-centered transition metal excited states

Endicott, John F.; Ramasami, T.; Tamilarasan, R.; Lessard, Ronald B.; Ryu, Chong Kul; Brubaker, George R.

doi:10.1016/0010-8545(87)85032-4

Cited by 70 publications

(55 citation statements)

References 224 publications

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“…12), whereas for others is dramatically shorter at room temperature than it is at 77 K [18,74]. At the low temperature limit, phosphorescence and nonradiative deactivation are responsible for excited state relaxation.…”

Section: Photophysicsmentioning

confidence: 96%

“…For more exhaustive reviews the reader is directed to several authoritative sources [17,18,[41][42][43].…”

Section: Photochemistry and Photophysics Of Chromium(iii) Complexesmentioning

confidence: 99%

“…For more comprehensive discussions of the photochemistry and photophysics of transition metal complexes, mostly organized according to the identity of the specific metals, the reader is directed to several excellent reviews [13][14][15][16][17][18][19][20]. In addition, Balzani and Carassiti's monograph on the photochemistry of coordination compounds [21], as well as the multi-authored volume edited by Adamson and Fleischauer [22] remain excellent introductions to the subject nearly 40 years after their publication.…”

Section: Introductionmentioning

confidence: 99%

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Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices

Wagenknecht¹,

Ford²

2011

Coordination Chemistry Reviews

281

292

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Section: Photophysicsmentioning

confidence: 96%

“…For more exhaustive reviews the reader is directed to several authoritative sources [17,18,[41][42][43].…”

Section: Photochemistry and Photophysics Of Chromium(iii) Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices

Wagenknecht¹,

Ford²

2011

Coordination Chemistry Reviews

281

292

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“…The solvent can also play a role in dictating the orbital population of the Frank-Condon excited state for charge transfer transitions (7). Considering that there are no noticeable changes in the position or shape of the absorption spectrum bands for water-glycerol mixtures, it can be concluded that, in this case, the quantum yield variation results not from the solvent-induced perturbation of electronic states but from variation in the kinetic parameters that govern excited state deactivation.…”

Section: Physical Measurements and Proceduresmentioning

confidence: 96%

“…Particular emphasis has been placed on complexes of d6 transition metal ions, and among them Co(II1) complexes have historically been used as attractive model systems for such studies (2)(3)(4)(5)(6)(7)(8)(9). The classical approach to this phenomenon is concerned with the competition between geminate recombination and solvent cage escape.…”

Section: Introductionmentioning

confidence: 99%

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex

Lima¹,

Iha²

1996

Can. J. Chem.

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Abstract:The solvent composition and wavelength effects on the quantum yield of the photoinduced ring closure process of the [~e (~~) , ( t n ) ]~-complex (tn = 1.3-diaminopropane) were investigated. The reactivity was shown to be controlled by the macroscopic properties of water-glycerol mixtures. A sharp decrease in quantum yields with increasing medium viscosity was observed for all the irradiation wavelengths employed (3 13,334,365,404, and 434 nm). The observed quantum yields ranged from 0.24 (Ai, = 313 nm, 66.48 wt.% of acetonitrile) to 0.010 (Ai, = 404 or 434 nm, 61.85 wt.% of glycerol). The overall efficiency is a complex function of the dynamics of radical recombination and dissociation pathways. The proposed cage model for the deactivation dynamics of the excited states illustrates that the decrease in medium viscosity favors a diffusional escapeof the cyanide from the solvent cage.Key words: photochemistry, pentacyanoferrate(I1) complexes, solvent effect, wavelength effect.Resume : L'effet de la composition du solvant et de la longueur d'onde de l'excitation dans le rendement quantique du processus photoinduit de fermeture d'anneau du complexe [~e ( c~) , ( t n ) ]~-(tn = 1.3-diaminepropane) a Ct C etudiC. La reactivitC semble &tre controlCe par les proprietCs macroscopiques des mClanges de solvant eau-glycerol. Une dtcroissance abrupte dans le rendement quantique est observCe avec la variation de la viscositC du milieu, pour tous les longueurs d'onde d'irradiation employCes (3 13, 334,365,404 et 434 nm). Le rendement quantique observC varie de 0,24 (Ai, = 313 nm; 66,48% poids acktonitrile) a 0,010 (Ai, = 404 ou 434 nm; 61,85% poids glycerol). L'efficacitC totale est une fonction complexe de la dynamique des ttapes de dissociation et de recombinasion radicale. Le modCle cage propost pour la dynamique de deactivation des Ctats excitCs montre que la dCcroissance dans la viscositC du milieu favorise la sortie de la cyanide de la cage du solvant.Mots elks : photochimie, complexes de pentacyanoferrate(II), effet du solvant, effet de la longueur d'onde de l'excitation,

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Primary Photoprocesses in Transition Metal Complexes

Forster

1991

Advances in Photochemistry

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Structure and reactivity of the metal-centered transition metal excited states

Cited by 70 publications

References 224 publications

Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices

Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex

Primary Photoprocesses in Transition Metal Complexes

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Structure and reactivity of the metal-centered transition metal excited states

Cited by 70 publications

References 224 publications

Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices

Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)5(tn)]3− complex

Primary Photoprocesses in Transition Metal Complexes

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Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex