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

作者：de Hatten Xavier; Bell Nicholas; Yufa Nataliya; Christmann Gabriel; Nitschke Jonathan R^*

来源：Journal of the American Chemical Society, 2011, 133(9): 3158-3164.

DOI：10.1021/ja110575s

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 degrees 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 (CuN4)-N-I cross-links as the equilibria 2[(CuN2P2)-N-I]reversible arrow [(CuN4)-N-I] + [CuPn](+) + (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.

• 出版日期2011-3-9