Alteration of Intraligand Donor-Acceptor Interactions Through Torsional Connectivity in Substituted Re-dppz Complexes

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

doi:10.1021/acs.inorgchem.7b01710

Alteration of Intraligand Donor-Acceptor Interactions Through Torsional Connectivity in Substituted Re-dppz Complexes

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

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

14 Citations (Scopus)

Abstract

The ground- and excited-state properties of a series of [ReCl(CO)₃(dppz)] complexes with substituted donor groups were investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituents allowed the effects on the photophysical properties to be characterized though both computational and spectroscopic techniques, including time-dependent density functional theory and resonance Raman and time-resolved infrared spectroscopy. The ground-state optical properties show significant variation as a result of donor group modulation, with an increased angle between the donor and acceptor blue-shifting and depleting the intensity of the lowest-energy transition, which is consistently intraligand charge transfer (ILCT) in nature. However, across all complexes studied there was minimal perturbation to the excited-state properties and dynamics. Three excited states on the picosecond, nanosecond, and microsecond time scales were observed in all cases, corresponding to ¹ILCT, ³ππ∗, and ³ILCT, respectively.

Original language	English
Pages (from-to)	12967-12977
Number of pages	11
Journal	Inorganic Chemistry
Volume	56
Issue number	21
DOIs	https://doi.org/10.1021/acs.inorgchem.7b01710
Publication status	Published - 6 Nov 2017

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.7b01710

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title = "Alteration of Intraligand Donor-Acceptor Interactions Through Torsional Connectivity in Substituted Re-dppz Complexes",

abstract = "The ground- and excited-state properties of a series of [ReCl(CO)3(dppz)] complexes with substituted donor groups were investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituents allowed the effects on the photophysical properties to be characterized though both computational and spectroscopic techniques, including time-dependent density functional theory and resonance Raman and time-resolved infrared spectroscopy. The ground-state optical properties show significant variation as a result of donor group modulation, with an increased angle between the donor and acceptor blue-shifting and depleting the intensity of the lowest-energy transition, which is consistently intraligand charge transfer (ILCT) in nature. However, across all complexes studied there was minimal perturbation to the excited-state properties and dynamics. Three excited states on the picosecond, nanosecond, and microsecond time scales were observed in all cases, corresponding to 1ILCT, 3ππ∗, and 3ILCT, respectively.",

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

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.7b01710",

language = "English",

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AU - Adams, Bethany S.

AU - Shillito, Georgina E.

AU - Van Der Salm, Holly

AU - Horvath, Raphael

AU - Larsen, Christopher B.

AU - Sun, Xue Zhong

AU - Lucas, Nigel T.

AU - George, Michael W.

AU - Gordon, Keith C.

PY - 2017/11/6

Y1 - 2017/11/6

N2 - The ground- and excited-state properties of a series of [ReCl(CO)3(dppz)] complexes with substituted donor groups were investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituents allowed the effects on the photophysical properties to be characterized though both computational and spectroscopic techniques, including time-dependent density functional theory and resonance Raman and time-resolved infrared spectroscopy. The ground-state optical properties show significant variation as a result of donor group modulation, with an increased angle between the donor and acceptor blue-shifting and depleting the intensity of the lowest-energy transition, which is consistently intraligand charge transfer (ILCT) in nature. However, across all complexes studied there was minimal perturbation to the excited-state properties and dynamics. Three excited states on the picosecond, nanosecond, and microsecond time scales were observed in all cases, corresponding to 1ILCT, 3ππ∗, and 3ILCT, respectively.

AB - The ground- and excited-state properties of a series of [ReCl(CO)3(dppz)] complexes with substituted donor groups were investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituents allowed the effects on the photophysical properties to be characterized though both computational and spectroscopic techniques, including time-dependent density functional theory and resonance Raman and time-resolved infrared spectroscopy. The ground-state optical properties show significant variation as a result of donor group modulation, with an increased angle between the donor and acceptor blue-shifting and depleting the intensity of the lowest-energy transition, which is consistently intraligand charge transfer (ILCT) in nature. However, across all complexes studied there was minimal perturbation to the excited-state properties and dynamics. Three excited states on the picosecond, nanosecond, and microsecond time scales were observed in all cases, corresponding to 1ILCT, 3ππ∗, and 3ILCT, respectively.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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Alteration of Intraligand Donor-Acceptor Interactions Through Torsional Connectivity in Substituted Re-dppz Complexes

Abstract

ASJC Scopus subject areas

UN SDGs

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