Synthesis and Optical Characterization of Polydiacetylenes Containing Carboxylic Acid, Carbamate, Phosphonium, and Quaternary Ammonium Functionalities

Abstract

Symmetrically substituted 1,3-diynes, X(CH2)nC⋮CC⋮C(CH2)nX (X = Et2N; n = 4, 9; 1d,e) have been prepared from the appropriate bis-tosylates (X = OSO2C6H4Me-p; 1b,c) and diethylamine, and one such derivative has been converted into a bis-quaternary ammonium salt (X = N+Et2MeI-; n = 4; 1f) and an ammonium sulfonate inner salt (X = N+Et2(CH2)3SO3-; n = 4; 1g), respectively. Three bis-phosphonium salts, X(CH2)nC⋮CC⋮C(CH2)nX (X = P+Ph3Br-; n = 4, 9, 3; 1h−j), were synthesized from 1,4-bis(bromoalkyl)-1,3-diynes and the appropriate phosphine derivative. The new diyne derivatives did not polymerize on exposure to γ-irradiation or electron beam irradiation in a Van der Graff linear accelerator. The tosylated polydiacetylene (PDA) derivative (2a, “PTS-12”) derived from 1b was treated with diethylamine to yield a tertiary amine-functionalized PDA derivative (2b), and the latter was allowed to react (separately) with methyl iodide and 1,3-propanesultone to give ionomeric PDAs 2c and 2d, respectively. The phosphinate...