Ionic polymers and oligomers with expanded π-conjugation system derived from through-space interaction in piperazinium ring

Reactions of N-(2,4-dinitrophenyI)-4-arylpyridinium chlorides (aryl (Ar) = phenyl and 4-pyridyl) with piperazines caused the ring opening of the pyridinium ring and yielded polymers that consisted of 5-piperazinium-3-aryl-penta-2,4-dienylideneammonium chloride units [-N(CH(R)CH2)(2)N+(Cl-)=CH CH=C(Ar)-CH=CH-, R=H, Me, and phenyl]. However, the same reactions occurring in the presence of piperidine yielded oligomers that consisted of 5-piperazinium-3-aryl-penta-2,4-dienylideneammonium chloride units having piperidine and/or piperazine rings at both ends. H-1 NMR spectra suggested that pi-electrons of the penta-2,4-dienylideneammonium group of the polymers and the oligomers were delocalized. UV-vis measurements revealed that the it-conjugation system expanded along the polymer and oligomer chains due to the orbital interaction between electrons on the two nitrogen atoms of the piperazinium ring. Conversion of the piperazinium ring from the boat form to the chair form caused decrease in the it-conjugation length. The rate constants of the conversion of the oligomers depended on their chain lengths. The surface of pellets that were molded from the polymers and oligomers exhibited metallic luster. These polymers and oligomers underwent electrochemical oxidation in solution. (C) 2010 Elsevier Ltd. All rights reserved.