价
化学
三合会(社会学)
接受者
电荷(物理)
结晶学
立体化学
凝聚态物理
精神分析
心理学
语言学
量子力学
物理
哲学
作者
Keishiro Tahara,Haruya KOYAMA,Mamoru Fujitsuka,Ken Tokunaga,Xu Lei,Tetsuro Majima,Jun‐ichi Kikuchi,Yoshiki Ozawa,Masaaki Abe
标识
DOI:10.1021/acs.joc.9b00836
摘要
In this study, we report the generation of new mixed-valence (MV) subspecies with charge-separated (CS) characters from an unsymmetrical acceptor-donor-donor (A-D-D) triad. The triad was synthesized by attaching a dimesitylboryl group (A) to a D-D conjugate that consisted of triarylamine (NAr3) units. The MV radical cation, obtained by chemical oxidation of the triad, exhibited a strong intervalence charge transfer (IVCT) absorption derived from the bis(NAr3)•+ moiety in the near-IR region. The charge-separated MV (CSMV) state, obtained by photoexcitation of the triad, caused a blue shift in IVCT energy in the femtosecond transient absorption spectra, reflecting a bias of positive charge distributions to the D end site. This resulted from increased electron density at the A site and restructuring of the central D site from NAr3 to NAr2 sites. Interestingly, any shift in the IVCT energy that was caused by the polarity of the solvent was minimal, reflecting the unique characteristics of the CSMV state. These findings represent the first detailed analysis of the CSMV state, including a comparison with conventional MV states. Therefore, this work provides new insights into counterion-free MV systems and their applications in molecular devices.
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