Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes: Driving Force Is the Dominant Factor in Controlling Lifetime

Jonathan E. Barnsley; Georgina E. Shillito; Christopher B. Larsen; Holly Van Der Salm; Raphael Horvath; Xue Zhong Sun; Xue Wu; Michael W. George; Nigel T. Lucas; Keith C. Gordon

doi:10.1021/acs.inorgchem.9b00792

Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes: Driving Force Is the Dominant Factor in Controlling Lifetime

Jonathan E. Barnsley, Georgina E. Shillito, Christopher B. Larsen, Holly Van Der Salm, Raphael Horvath, Xue Zhong Sun, Xue Wu, Michael W. George, Nigel T. Lucas, Keith C. Gordon

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

16 Citations (Scopus)

Abstract

A transition-metal-based donor-(linker)-acceptor system can produce long-lived charge transfer excited states using visible excitation wavelengths. The ground- and excited-state photophysical properties of a series of [ReCl(CO)₃(dppz-(linker)-TPA)] complexes, with varying donor and acceptor energies, have been systematically studied using spectroscopic techniques (both vibrational and electronic) supported by computational chemistry. The long-lived excited state is ³ILCT in nature for all complexes studied, characterized through transient absorption and emission, transient resonance Raman (TR²), and time-resolved infrared (TRIR) spectroscopy and TDDFT calculations. Modulation of the donor and acceptor energies results in changes of the ³ILCT lifetime by 1 order of magnitude, ranging from 6.1(±1) μs when a diphenylamine donor is used to 0.6(±0.2) μs when a triazole linker and triphenylamine donor is used. The excited-state lifetime may be rationalized by consideration of the driving force within the framework of Marcus theory and appears insensitive to the nature of the linker.

Original language	English
Pages (from-to)	9785-9795
Number of pages	11
Journal	Inorganic Chemistry
Volume	58
Issue number	15
DOIs	https://doi.org/10.1021/acs.inorgchem.9b00792
Publication status	Published - 5 Aug 2019

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Barnsley, J. E., Shillito, G. E., Larsen, C. B., Van Der Salm, H., Horvath, R., Sun, X. Z., Wu, X., George, M. W., Lucas, N. T., & Gordon, K. C. (2019). Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes: Driving Force Is the Dominant Factor in Controlling Lifetime. Inorganic Chemistry, 58(15), 9785-9795. https://doi.org/10.1021/acs.inorgchem.9b00792

@article{8240bf67258c4481ae82bfecee9546e9,

title = "Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes: Driving Force Is the Dominant Factor in Controlling Lifetime",

abstract = "A transition-metal-based donor-(linker)-acceptor system can produce long-lived charge transfer excited states using visible excitation wavelengths. The ground- and excited-state photophysical properties of a series of [ReCl(CO)3(dppz-(linker)-TPA)] complexes, with varying donor and acceptor energies, have been systematically studied using spectroscopic techniques (both vibrational and electronic) supported by computational chemistry. The long-lived excited state is 3ILCT in nature for all complexes studied, characterized through transient absorption and emission, transient resonance Raman (TR2), and time-resolved infrared (TRIR) spectroscopy and TDDFT calculations. Modulation of the donor and acceptor energies results in changes of the 3ILCT lifetime by 1 order of magnitude, ranging from 6.1(±1) μs when a diphenylamine donor is used to 0.6(±0.2) μs when a triazole linker and triphenylamine donor is used. The excited-state lifetime may be rationalized by consideration of the driving force within the framework of Marcus theory and appears insensitive to the nature of the linker.",

author = "Barnsley, \{Jonathan E.\} and Shillito, \{Georgina E.\} and Larsen, \{Christopher B.\} and \{Van Der Salm\}, Holly and Raphael Horvath and Sun, \{Xue Zhong\} and Xue Wu and George, \{Michael W.\} and Lucas, \{Nigel T.\} and Gordon, \{Keith C.\}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = aug,

day = "5",

doi = "10.1021/acs.inorgchem.9b00792",

language = "English",

volume = "58",

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journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

number = "15",

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Barnsley, JE, Shillito, GE, Larsen, CB, Van Der Salm, H, Horvath, R, Sun, XZ, Wu, X, George, MW, Lucas, NT & Gordon, KC 2019, 'Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes: Driving Force Is the Dominant Factor in Controlling Lifetime', Inorganic Chemistry, vol. 58, no. 15, pp. 9785-9795. https://doi.org/10.1021/acs.inorgchem.9b00792

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T1 - Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes

T2 - Driving Force Is the Dominant Factor in Controlling Lifetime

AU - Barnsley, Jonathan E.

AU - Shillito, Georgina E.

AU - Larsen, Christopher B.

AU - Van Der Salm, Holly

AU - Horvath, Raphael

AU - Sun, Xue Zhong

AU - Wu, Xue

AU - George, Michael W.

AU - Lucas, Nigel T.

AU - Gordon, Keith C.

PY - 2019/8/5

Y1 - 2019/8/5

N2 - A transition-metal-based donor-(linker)-acceptor system can produce long-lived charge transfer excited states using visible excitation wavelengths. The ground- and excited-state photophysical properties of a series of [ReCl(CO)3(dppz-(linker)-TPA)] complexes, with varying donor and acceptor energies, have been systematically studied using spectroscopic techniques (both vibrational and electronic) supported by computational chemistry. The long-lived excited state is 3ILCT in nature for all complexes studied, characterized through transient absorption and emission, transient resonance Raman (TR2), and time-resolved infrared (TRIR) spectroscopy and TDDFT calculations. Modulation of the donor and acceptor energies results in changes of the 3ILCT lifetime by 1 order of magnitude, ranging from 6.1(±1) μs when a diphenylamine donor is used to 0.6(±0.2) μs when a triazole linker and triphenylamine donor is used. The excited-state lifetime may be rationalized by consideration of the driving force within the framework of Marcus theory and appears insensitive to the nature of the linker.

AB - A transition-metal-based donor-(linker)-acceptor system can produce long-lived charge transfer excited states using visible excitation wavelengths. The ground- and excited-state photophysical properties of a series of [ReCl(CO)3(dppz-(linker)-TPA)] complexes, with varying donor and acceptor energies, have been systematically studied using spectroscopic techniques (both vibrational and electronic) supported by computational chemistry. The long-lived excited state is 3ILCT in nature for all complexes studied, characterized through transient absorption and emission, transient resonance Raman (TR2), and time-resolved infrared (TRIR) spectroscopy and TDDFT calculations. Modulation of the donor and acceptor energies results in changes of the 3ILCT lifetime by 1 order of magnitude, ranging from 6.1(±1) μs when a diphenylamine donor is used to 0.6(±0.2) μs when a triazole linker and triphenylamine donor is used. The excited-state lifetime may be rationalized by consideration of the driving force within the framework of Marcus theory and appears insensitive to the nature of the linker.

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Generation of Microsecond Charge-Separated Excited States in Rhenium(I) Diimine Complexes: Driving Force Is the Dominant Factor in Controlling Lifetime

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