SYNTHESIS AND OPTICAL CHARACTERIZATION OF POLYDIACETYLENES CONTAININGCARBOXYLIC-ACID, CARBAMATE, PHOSPHONIUM, AND QUATERNARY AMMONIUM FUNCTIONALITIES

Symmetrically substituted 1,3-diynes, X(CH2)(n)C drop C-C drop C(CH2)( n)X (X = Et(2)N; n = 4, 9; 1d,e) have been prepared from the appropria te bis-tosylates (X = OSO(2)C(6)H(4)Me-p; 1b,c) and diethylamine, and one such derivative has been converted into a bis-quaternary ammonium salt (X = N(+)Et(2)MeI(-); n = 4; 1f) and an ammonium sulfonate inner salt (X = N(+)Et(2)(CH2)(3)SO3-; n = 4; 1g), respectively. Three bis-p hosphonium salts, X(CH2)(n)C drop C-C drop C(CH2)(n)X (X = P(+)Ph(3)Br (-); n = 4, 9, 3; 1h-j), were synthesized from 1,4-bis(bromoalkyl)-1,3 -diynes and the appropriate phosphine derivative. The new diyne deriva tives did not polymerize on exposure to gamma-irradiation or electron beam irradiation in a Van der Graff linear accelerator. The tosylated polydiacetylene (PDA) derivative (2a, ''PTS-12'') derived from Ib was treated with diethylamine to yield a tertiary amine-functionalized PDA derivative (2b), and the latter was allowed to react (separately) wit h methyl iodide and 1,3-propanesultone to give ionomeric PDAs 2c and 2 d, respectively. The phosphinated PDA (2e) was synthesized from PTS-12 (2a) and diphenylphosphinyllithium or -potassium, and this material w as used to prepare the PDA phosphonium salt 2f. The nonlinear optical properties of selected new PDAs (2c,d,f), as well as some known PDAs, were evaluated by means of the z-scan technique. The magnitudes of two -photon absorption coefficients (beta) were determined and are discuss ed.