Synthesis, crystal structure and photochromism of new diarylethenes with a benzene moiety.
Three unsymmetrical diarylethenes with both thiophene and benzene moieties were synthesized. Their crystal structures and photochromic features were investigated systematically to elucidate the substituent effects of the terminal phenyl group on photochromism. Computational studies were performed to provide further insight into their frontier molecular orbitals and spatial distributions of electronic density. Each compound exhibited favorable photochromism in hexane and functioned as notable fluorescent photo-switches with fluorescence quenching efficiency of ∼96% induced by the intensity change of UV/vis light. Among the three diarylethenes, the cyano group on the terminal phenyl group significantly decreased the distance of the two reactive carbon atoms and strengthened the intermolecular hydrogen bond stacking interactions, resulting in improved stability in crystal state. Furthermore, it exhibited a red-shifted absorption maximum, an enhanced molar absorption coefficient, cyclization quantum yield, and fluorescence quantum yield in solution.
Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, PR China.
Congbin
C
Fan
Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, PR China. Electronic address: pushouzhi@tsinghua.org.cn.
Shouzhi
S
Pu
Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, PR China.
Gang
G
Liu
D001554:Benzene / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005030:Ethylenes / Q000138:chemical synthesis / Q000737:chemistry*; D005453:Fluorescence; D008958:Models, Molecular; D013050:Spectrometry, Fluorescence; D013876:Thiophenes / Q000138:chemical synthesis / Q000737:chemistry
D005030:Ethylenes; D013876:Thiophenes; C036216:ethylene; D001554:Benzene
Crystal structure; Diarylethene; Fluorescence switch; Photochromism; Substituent effect