Topochemical polymerization of unsymmetrical aryldiacetylene supramolecules with nitrophenyl substituents utilizing C–H⋯π interactions

Abstract

Diacetylenes are versatile building blocks, in which many functional groups can be incorporated for the construction of new materials with desirable properties. In this study, 6-(p or m-nitrophenyl)-3,5-hexadiyne-1-ol (4a or 4b) containing nitrophenyl groups (host) and 2-hydroxyethyl groups (guest) in different diacetylene terminals were designed to establish an ordered supramolecular assembly that is complied with the strict requirements for the topochemical polymerization of diacetylenes. Crystal film and bulk crystals of compound 4b were obtained successfully by cast film and re-precipitation methods. Both of these could photopolymerize to the corresponding regular poly(diacetylene) polymer, as evidenced by UV-vis, IR, FL and Raman spectroscopy. The electrochemical properties and behaviors of 4a and 4b were also investigated, and the results show that the differences between the para and meta positions of the mono-phenylacetylene substituents probably result from the topochemical polymerization. Thus, m-nitrophenylbutadiyne derivatives with sizeable C–H⋯π interactions seemed to be effective for the formation of a polymerizable packing, which is appropriate for topochemical polymerization.