TY - JOUR
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.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
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.
UR - http://www.scopus.com/inward/record.url?scp=85070915824&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b00792
DO - 10.1021/acs.inorgchem.9b00792
M3 - Article
C2 - 31314505
AN - SCOPUS:85070915824
SN - 0020-1669
VL - 58
SP - 9785
EP - 9795
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 15
ER -