摘要
Unexpected transition metal(TM)-π interaction enhanced fluorescence in Cu-π-diborene complexes is a novel phenomenon compared with other metal enhanced fluorescence. In order to discover the mechanism, theoretical investigation was carried out for Cu-π-diborene as well as diborene. Simulation results show the main decay method in diborene and Cu-π-diborene are internal conversion(IC) and fluorescence(FL), respectively. TM-π interaction leads to larger HOMO-LUMO gap of Cu-π-diborene than that of the free diborene, which results in lower IC rates and makes them smaller than the FL rates. At the same time, ISC rates are always smaller than IC and FL rates, which cause enhanced fluorescence of Cu-π-diborene. More interestingly, even though Cu-π-diborene shows enhanced fluorescence, intersystem crossing(ISC) in Cu-π-diborene is enhanced from diborene. The theoretical analysis shows the competition among IC, FL and ISC is the key factor for TM-π interactions enhanced fluorescence, which also shows that cation-π complexes have potential to be used as luminescent probes.
作者
ZHANG Zhi-Yong
ZHANG Zhong-Zhi
LUO Yi-Jing
ZHANG Guang-Qing
张志勇;张忠智;罗一菁;张广清(Laboratory of Heavy Oil Processing,College of Chemical Engineering and Environment,China University of Petroleum,Beijing 102249,China;School of Mechanical,Materials&Mechatronic Engineering,University of Wollongong,Wollongong NSW2S22,Australia)
基金
Supported by the National Natural Science Foundation of China (No. 51634008)
National Science and Technology Major Project (No. 2017ZX05009-004)。
