PtII Diimine Chromophores with Perfluorinated Thiolate Ligands: Nature and Dynamics of the Charge-Transfer-to-Diimine Lowest Excited State

Julia A. Weinstein, Alexander J. Blake, E. Stephen Davies, Adrienne L. Davis, Michael W. George, David Grills, Igor V. Lileev, Alexander M. Maksimov, Pavel Matousek, Mikhail Ya Mel'Nikov, Anthony W. Parker, Vyacheslav E. Platonov, Michael Towrie, Claire Wilson, Natalia N. Zheligovskaya

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Abstract

The synthesis of new PtII diimine complexes bearing perfluorinated thiolate ligands, PtII(NN)(4-X-C6F 4-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(φ)/S(p)/Pt(d) orbitals and that the LUMO is largely localized on the φ* (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-C6F 4-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.

Original languageEnglish
Pages (from-to)7077-7085
Number of pages9
JournalInorganic Chemistry
Volume42
Issue number22
DOIs
Publication statusPublished - Nov 3 2003

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Chromophores
Excited states
chromophores
Charge transfer
charge transfer
Ligands
ligands
vibration
excitation
Bearings (structural)
orbitals
Fluorine
augmentation
fluorine
Raman scattering
Infrared spectroscopy
electron transfer
infrared spectroscopy
analogs
Raman spectra

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

PtII Diimine Chromophores with Perfluorinated Thiolate Ligands : Nature and Dynamics of the Charge-Transfer-to-Diimine Lowest Excited State. / Weinstein, Julia A.; Blake, Alexander J.; Davies, E. Stephen; Davis, Adrienne L.; George, Michael W.; Grills, David; Lileev, Igor V.; Maksimov, Alexander M.; Matousek, Pavel; Mel'Nikov, Mikhail Ya; Parker, Anthony W.; Platonov, Vyacheslav E.; Towrie, Michael; Wilson, Claire; Zheligovskaya, Natalia N.

In: Inorganic Chemistry, Vol. 42, No. 22, 03.11.2003, p. 7077-7085.

Research output: Contribution to journalArticle

Weinstein, JA, Blake, AJ, Davies, ES, Davis, AL, George, MW, Grills, D, Lileev, IV, Maksimov, AM, Matousek, P, Mel'Nikov, MY, Parker, AW, Platonov, VE, Towrie, M, Wilson, C & Zheligovskaya, NN 2003, 'PtII Diimine Chromophores with Perfluorinated Thiolate Ligands: Nature and Dynamics of the Charge-Transfer-to-Diimine Lowest Excited State', Inorganic Chemistry, vol. 42, no. 22, pp. 7077-7085. https://doi.org/10.1021/ic026286l
Weinstein, Julia A. ; Blake, Alexander J. ; Davies, E. Stephen ; Davis, Adrienne L. ; George, Michael W. ; Grills, David ; Lileev, Igor V. ; Maksimov, Alexander M. ; Matousek, Pavel ; Mel'Nikov, Mikhail Ya ; Parker, Anthony W. ; Platonov, Vyacheslav E. ; Towrie, Michael ; Wilson, Claire ; Zheligovskaya, Natalia N. / PtII Diimine Chromophores with Perfluorinated Thiolate Ligands : Nature and Dynamics of the Charge-Transfer-to-Diimine Lowest Excited State. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 22. pp. 7077-7085.
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abstract = "The synthesis of new PtII diimine complexes bearing perfluorinated thiolate ligands, PtII(NN)(4-X-C6F 4-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(φ)/S(p)/Pt(d) orbitals and that the LUMO is largely localized on the φ* (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-C6F 4-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.",
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AU - Weinstein, Julia A.

AU - Blake, Alexander J.

AU - Davies, E. Stephen

AU - Davis, Adrienne L.

AU - George, Michael W.

AU - Grills, David

AU - Lileev, Igor V.

AU - Maksimov, Alexander M.

AU - Matousek, Pavel

AU - Mel'Nikov, Mikhail Ya

AU - Parker, Anthony W.

AU - Platonov, Vyacheslav E.

AU - Towrie, Michael

AU - Wilson, Claire

AU - Zheligovskaya, Natalia N.

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N2 - The synthesis of new PtII diimine complexes bearing perfluorinated thiolate ligands, PtII(NN)(4-X-C6F 4-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(φ)/S(p)/Pt(d) orbitals and that the LUMO is largely localized on the φ* (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-C6F 4-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.

AB - The synthesis of new PtII diimine complexes bearing perfluorinated thiolate ligands, PtII(NN)(4-X-C6F 4-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(φ)/S(p)/Pt(d) orbitals and that the LUMO is largely localized on the φ* (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-C6F 4-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.

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