A Rational Approach to the Preparation of <i>Poly</i>dipyridyldiacetylenes: An Exercise in Crystal Design

Abstract

Crystals have been designed for the purpose of carrying out the topochemical polymerization of two isomeric dipyridyldiacetylenes, 1,4-di(pyrdin-3-yl)buta-1,3-diyne (3-pda) and 1,4-di(pyrdin-4-yl)buta-1,3-diyne (4-pda). A successful polymerization depends on achieving a monomer spacing, dm, of 4.90 Å with a close contact R1,4, between the reacting atoms, C1−C4‘, of neighboring diacetylenes. A series of five oxalamide dicarboxylic acid host molecules were chosen for the study since they were known to form hydrogen-bond networks with spacings near the required 4.90 Å. Five host molecules and two diacetylene guests should have given 10 cocrystals, but only eight were successfully obtained. The best parameters were found for the cocrystal of the 4-pyridyl isomer, 4-pda, with the oxalamide of glycine, 1-ox. The repeat distance, dm, was 4.93 Å with an R1,4 contact of 3.62 Å. The 4-pda:1-ox cocrystals were stable to heat, but ultraviolet irradiation polymerized the compound with an isolated yield of 61%.