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  • 03월 02일 17시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

제109회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Probing Ground-to-CT State Electronic Coupling by Ultrafast Visible-Pump/Mid-IR-Probe Spectroscopy; Application to Sensitizer-Semiconductor Interfacial Electronic Coupling

2012년 2월 16일 17시 38분 09초
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목 10시 : 30분
물리화학 - Energy conversion and solar cell: physical chemist's view
저자 및
상명대학교 화학과, Korea

New pi-stacked [Ru(tpy)2]2+ (T_T)-benzoquinone (Q) donor-acceptor (D-A) systems, [Ru(6-(2-cyclohexa-2’,5’-diene-1,4-dione)-2,2’:6’,2”-terpyridine)(2,2’:6’,2”-terpyridine)][PF6]2 (TQ_T), have been synthesized and characterized. Orthogonal alignment of Q to the tpy ligand imposes this unit juxtaposed cofacially on the central pyridyl ring in another tpy with a typical van der Waals distance. The low energy electronic absorptions of these complexes are mainly metal-to-ligand charge transfer (MLCT) in nature, similar to that observed in T_T benchmark system, and do not exhibit distinguishable metal-to-Q charge transfer (MQCT) absorption in spite of the proximal location of the electron acceptor unit (Q) to the electron donor unit (T_T). Due to the negligible intensity of MQCT bands, evaluation of HDA between ground and lowest energy MQCT states are not available through conventional Mulliken-Hush analysis. For such systems, HDA values were successfully evaluated from the relative difference (xi) of the carbonyl stretching frequency between the neutral Q and its one electron radical anion, which was determined by an ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. TrIR results showed that the partial charge localized on Q moiety in the MQCT state was ~ -0.97e and the corresponding HDA was ~1600 cm-1. Extending this methodoly provides useful information regarding sensitizer-semiconductor interfacial electronic coupling in dye-sensitized solar cell, which cannot be precisely evaluated by conventional electron transfer rate measurement.