Affiliation: | 1. Graduate School of Chemical Sciences and Engineering, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, 060-0810 Japan;2. Graduate School of Chemical Sciences and Engineering, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, 060-0810 Japan Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, 060-0810 Japan Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, 060-0810 Japan |
Abstract: | 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. |