Photoinduced Pyramidal Inversion Behavior of Phosphanes Involved with Aggregation-Induced Emission Behavior

被引:10
|
作者
Machida, Takashi [1 ]
Iwasa, Takeshi [1 ,2 ,3 ]
Taketsugu, Tetsuya [1 ,2 ,3 ]
Sada, Kazuki [1 ,2 ]
Kokado, Kenta [1 ,2 ,4 ]
机构
[1] Hokkaido Univ, Grad Sch Chem Sci & Engn, Kita Ku, Kita 10 Nishi 8, Sapporo, Hokkaido 0600810, Japan
[2] Hokkaido Univ, Fac Sci, Dept Chem, Kita Ku, Kita 10 Nishi 8, Sapporo, Hokkaido 0600810, Japan
[3] Hokkaido Univ, Inst Chem React Design & Discovery WPI ICReDD, Kita Ku, Kita 10 Nishi 8, Sapporo, Hokkaido 0600810, Japan
[4] JST PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 3320012, Japan
关键词
aggregation-induced emission; chirality; phosphanes; photochemistry; pyramidal inversion; TRIARYLPHOSPHINE RADICAL CATIONS; STEREOGENIC PHOSPHORUS-COMPOUNDS; CONICAL INTERSECTION; ELECTRONIC-STRUCTURE; BASIS-SETS; ENERGY; BARRIER; PHOSPHINES; MECHANISM; LUMINESCENCE;
D O I
10.1002/chem.202000264
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Aggregation-induced emission (AIE) is a fascinating phenomenon because of the applications of luminescent materials in the aggregated state, which exploit the large structural changes of the molecules in the excited state. Recently, it was reported that triphenylphosphane derivatives show AIE behavior in which they undergo potentially large structural changes in the excited state. Inspired by this report, photoinduced pyramidal inversion behavior of phosphanes was investigated. In photochemical experiments, the prepared P-stereogenic phosphanes exhibited photoracemization in dilute solution, and a negative correlation was observed between the photoracemization and the AIE phenomenon. Theoretical computations revealed that the inversion barrier in the excited state was much smaller than that in the ground state. This is the first report on the photoinduced pyramidal inversion behavior of phosphanes, which will provide new and unexplored applications.
引用
收藏
页码:8028 / 8034
页数:7
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