Pt-II diimine chromophores with perfluorinated thiolate ligands: Nature and dynamics of the charge-transfer-to-diimine lowest excited state

Pt-II diimine chromophores with perfluorinated thiolate ligands: Nature and dynamics of the charge-transfer-to-diimine lowest excited state Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669

Output data

Year: 2003, Volume: 42, Number: 22, Pages: 7077-7085 Pages count : DOI: 10.1021/ic026286l

Authors

Weinstein JA , Blake AJ , Davies ES , Davis AL , George MW , Grills DC , Lileev IV , Maksimov AM , Matousek P , Mel'nikov MY , Parker AW , Platonov VE , Towrie M , Wilson C , Zheligovskaya NN

Affiliations

1	(Данные Web of science) Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England
2	(Данные Web of science) Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119899, Russia
3	(Данные Web of science) Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia
4	(Данные Web of science) Rutherford Appleton Lab, CCLRC, Didcot OX11 0QX, Oxon, England

The synthesis of new Pt-II diimine complexes bearing perfluorinated thiolate ligands, Pt-II(NN)(4-X-C6F4-S)(2), where NN = 2,2'-bipyridine or 1,10-phenanthroline and X = F or CN, is reported, together with an investigation of the nature and dynamics of their lowest excited states. A combined UV-vis, (spectro)electrochemical, resonance Raman, and time-resolved infrared (TRIR) study has suggested that the HOMO is mainly composed of thiolate(pi)/S(p)/Pt(d) orbitals and that the LUMO is largely localized on the pi(*) (diimine) orbital, thus revealing the {charge-transfer-to-diimine} nature of the lowest excited state. An enhancement of the thiolate ring vibrations, C-F vibrations, and the vibration of the CN-substituent on the thiolate moiety was observed in the resonance Raman spectra, whereas no such enhancement was seen for the nonfluorinated analogues. Thus, the introduction of fluorine substituents on the thiolate moiety probably leads to a more pronounced contribution of the intrathiolate modes to the HOMO compared to the analogous complexes with nonfluorinated thiolates. Furthermore, the introduction of the p-CN group into the thiolate moiety has allowed the dynamics of the lowest excited state of Pt(bpy)(4-CN-C6F4-S)(2) to be monitored by picosecond TRIR spectroscopy. The dynamics of the lowest {charge-transfer-to-diimine} excited state are governed by ca. 2-ps vibrational cooling and 35-ps back electron transfer.

Weinstein J. , Blake A. , Davies E. , Davis A. , George M. , Grills D. , Lileev I. , Maksimov A. , Matousek P. , Mel'nikov M. , Parker A. , Platonov V. , Towrie M. , Wilson C. , Zheligovskaya N.
Pt-II diimine chromophores with perfluorinated thiolate ligands: Nature and dynamics of the charge-transfer-to-diimine lowest excited state
Inorganic Chemistry. 2003. V.42. N22. P.7077-7085. DOI: 10.1021/ic026286l WOS Scopus РИНЦ

Published print:

Nov 1, 2003

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