Main content area

Molecular Engineering of Mechanochromic Materials by Programmed C–H Arylation: Making a Counterpoint in the Chromism Trend

Wu, Jie, Cheng, Yangyang, Lan, Jingbo, Wu, Di, Qian, Shengyou, Yan, Lipeng, He, Zhen, Li, Xiaoyu, Wang, Kai, Zou, Bo, You, Jingsong
Journal of the American Chemical Society 2016 v.138 no.39 pp. 12803-12812
chemical bonding, engineering, fluorescent dyes, isomers, prediction, pyrimidines, screening
The development of facile methods for screening organic functional molecules through C–H bond activation is a revolutionary trend in materials research. The prediction of mechanochromism as well as mechanochromic trends of luminogens is an appealing yet challenging puzzle. Here, we present a strategy for the design of mechanochromic luminogens based on the dipole moment of donor–acceptor molecules. For this purpose, a highly efficient route to 2,7-diaryl-[1,2,4]triazolo[1,5-a]pyrimidines (2,7-diaryl-TAPs) has been established through programmed C–H arylation, which unlocks a great opportunity to rapidly assemble a library of fluorophores for the discovery of mechanochromic regularity. Molecular dipole moment can be employed to explain and further predict the mechanochromic trends. The 2,7-diaryl-TAPs with electron-donating groups on the 2-aryl and electron-withdrawing groups on the 7-aryl possess a relatively small dipole moment and exhibit a red-shifted mechanochromism. When the two aryls are interchanged, the resulting luminogens have a relatively large dipole moment and display a blue-shifted mechanochromism. Seven pairs of isomers with opposite mechanochromic trends are presented as illustrative examples. The aryl-interchanged congeners with a bidirectional emission shift are structurally similar, which provides an avenue for understanding in-depth the mechanochromic mechanism.