A Dynamic Covalent, Luminescent Metallopolymer that Undergoes Sol-to-Gel Transition on Temperature Rise

Abstract

The condensation of linear diamine and dialdehyde subcomponents around copper(I) templates in the presence of bulky trioctylphosphine ancillary ligands gave a linear, conjugated polymeric material in DMSO solution. This polymer solution was observed to undergo sol-to-gel transition as the temperature was raised to 140 °C, in contrast with the behavior of most gel-forming polymers, which do so upon cooling. We attribute the sol-to-gel transition to the formation of Cu(I)N(4) cross-links as the equilibria 2[Cu(I)N(2)P(2)] ⇄ [Cu(I)N(4)] + [CuP(n)](+) + (4 - n)P favor the right-hand side at higher temperatures. The material was also observed to exhibit thermochromism and photoluminescence, with the color and intensity of both absorption and emission exhibiting temperature dependence. This material thus responds predictably to combinations of stimuli (heat, light, mechanical shear) in an interconnected way, as is required to generate complex function.