Constructing a mixed π-conjugated bridge to effectively enhance the nonlinear optical response in the Möbius cyclacene-based systems.
Using density functional theory computations, employing the concept of a mixed π-conjugated bridge can effectively improve the first hyperpolarizability (β0) of Möbius cyclacene (MC)-based systems with a D-π-A framework. This mixed π-conjugated bridge is constructed by applying a -(CH=CH)x-NH2 or -(CH=CH)x-NO2 chain to modify [8]MC, which can lead to a considerable β0 value (e.g. [8]MC-(CH=CH)12-NO2 (9.87 × 10(5) au) with only a certain chain length), much larger than the sole [8]MC (261 au) and the corresponding NH2/NO2-modified polyethylene chain with the same π-conjugated length. It is revealed that the substituent sites and the chain length can play a crucial role in improving β0 values of these MC-chain systems, where the β0 value can monotonically increase with increasing -(CH=CH)x- length, and the substituent electron-withdrawing -(CH=CH)x-NO2 chain is superior to the parallel electron-donating -(CH=CH)x-NH2. These appealing findings can provide valuable insights into the design of novel NLO materials based on MC.
The State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China. yugt@jlu.edu.cn w_chen@jlu.edu.cn xurihuang09@gmail.com.
Liwei
L
Chen
Guangtao
G
Yu
Wei
W
Chen
Chunyun
C
Tu
Xingang
X
Zhao
Xuri
X
Huang