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

Research output: Journal PublicationArticlepeer-review

8 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 languageEnglish
Pages (from-to)9785-9795
Number of pages11
JournalInorganic Chemistry
Volume58
Issue number15
DOIs
Publication statusPublished - 5 Aug 2019

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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