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  • 02월 19일 10시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

대한화학회 제121회 학술발표회 및 총회 A Highly Reactive Cobalt(IV)-Oxo Excited State with 0.6 ns Lifetime

2018년 2월 5일 22시 35분 08초
INOR.P-76 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
4월 19일 (목요일) 11:00~12:30
Inorganic Chemistry
저자 및
Claudio Saracini, Yong-Min Lee1, Shunichi Fukuzumi2,*, Wonwoo Nam3,*
Department of Chemistry and Nano Science, Ewha Womans University, Italy
1Research Institute for Basic Sciences, Ewha Womans University, Korea
2Graduate School of Science and Engineering, Meijo University, Japan
3Department of Chemistry, Ewha Womans University, Korea
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승인 1건
Excited states of synthetic complexes based on rare metals such as ruthenium, rhenium, osmium, technetium, and tungsten have been previously reported to exhibit emission upon photoexcitation of their related ground states and, in some cases, they exhibit long lifetime, like for the famous ruthenium(II) tris-bipyridine complex. In contrast, the reported excited states of transition-metal complexes based on earth-abundant metals, showed extremely short lifetimes which have, so far, strictly limited or precluded the utilization of their expected high reactivity. We introduce here the excited state of a high-valent earth-abundant transition metal-oxo complex, S1*, that was detected for the first time by femtosecond laser transient absorption spectroscopy and was generated from photoexcitation of the cobalt(IV)-oxo complex [(TAML)CoIV(O)]2– (1) (TAML = tetraamidomacrocyclic ligand). The excited state S1* exhibited a long lifetime, τ = 0.6(1) ns, and a high reactivity towards substrate oxidation such as intermolecular electron transfer oxidation of m-xylene and anisole. This method could be used as a new way to generate reactive excited states, like S1*, from high-valent earth-abundant transition metal-oxo complexes, like complex 1, that can be exploited to perform intermolecular electron transfer with organic substrates using the energy harvested from visible light; reactivity otherwise impossible to be achieved by the ground state.