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제124회 대한화학회 학술발표회, 총회 및 기기전시회 안내 X-ray Absorption Study of Photo-Induced Tautomeric Interconversion of Co-dioxolene complexes

등록일
2019년 9월 9일 13시 26분 18초
접수번호
1985
발표코드
PHYS.P-229 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
10월 17일 (목요일) 11:00~12:30
발표형식
포스터
발표분야
Physical Chemistry
저자 및
공동저자
Yujin Kim, Tae Kyu Kim*, Shunsuke Nozawa1, Shin-ichi Adachi1
Department of Chemistry, Yonsei University, Korea
1Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Japan, Japan
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승인 2건
The metal-dioxolene complex, showing redox isomerization have been actively investigated due to their potential application possibilities in the magnetic switch. In this work, we have performed picosecond time-resolved X-ray absorption spectroscopy (XAS) studies on the cobalt K-edge of two different Co-dioxolene complexes (Co(Cat-N-BQ)(Cat-N-SQ) and Co(tpy)(Cat-N-SQ)PF6, where Cat-N-BQ = 2-(2-hydroxy-3,5-ditert-butylphenyl-imino)-4,6-ditert-butylcyclohexa-3,5-dienone, Cat-N-SQ is the dianionic radical analogue, and tpy = 2,2′-6-2″- terpyridine) in toluene solution. 100 fs, 500 nm pump pulses initiate one-electron charge transfer from the radical semiquinonate ligand to the Co-metal center in the low-spin complexes. The subsequent electronic and geometrical changes associated with the formation of high-spin state of Co- dioxolene complexes are probed by 70 ps, 7.7 keV tunable X-ray pulses from Photon Factory Advanced Ring (PF-AR). Theoretical modeling of transient XAS spectra reveals that the bond-distances between Co and nearby ligand-atoms are lengthened in the high-spin state. These structural changes cause the spectral changes, which reflect altered hybridization of metal-3d, metal-4p, and ligand-2p orbitals accompanied by one-electron transfer process.

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