Alcohol-soluble bis(tpy)thiophenes: new building units for constitutional dynamic conjugated polyelectrolytes.

New building units (unimers) for metallo-supramolecular polymers 2,5-bis(2,2':6',2''-terpyridine-4'-yl)thiophene, M, and 5,5'-bis(2,2':6',2''-terpyridine-4'-yl)(2,2'-bithiophene), B, with ionic groups attached to thiophene rings are prepared by the modification of corresponding bromo-precursors and assembled with Zn(2+) and Fe(2+) ions into alcohol-soluble conjugated constitutional-dynamic polyelectrolytes (polyelectrolyte dynamers). Ionization of side groups only slightly affects the absorption spectra of unimers as well as dynamers but dramatically changes their solubility. Cyclic conformations of unimer molecules resulting from intramolecular interactions between tpy end-groups and cationic or polar (-CH2Br) side groups are proposed to explain the spectral conformity of the M- and B-type unimers and their dynamers and also inhibition of the ionization reaction with tpy end-groups.

Time-Resolved Transient Optical Absorption Study of Bis(terpyridyl)oligothiophenes and Their Metallo-Supramolecular Polymers with Zn(II) Ion Couplers.

α,ω-Bis(terpyridyl)oligothiophenes spontaneously assemble with Zn(II) ions giving conjugated constitutional dynamic polymers (dynamers) of the metallo-supramolecular class, which potentially might be utilized in optoelectronics. Their photophysical properties, which are of great importance in this field of application, are strongly influenced by the dynamic morphology. It was assessed in this study by using ultrafast pump-probe optical absorption spectroscopy.