The spontaneous, catalyst free polymerization of four monomers of the bis(pyridyl)acetylene and bis[(pyridyl)ethynyl]benzene types containing either 2-pyridyl or 4-pyridyl groups via activation with benzyl bromide leads to ionic π-conjugated polyacetylene-type polyelectrolytes (CPEs). All polymers are characterized by means of NMR, IR, UV/vis and photoluminescence spectroscopies, thermogravimetric analysis (TGA) and matrix assisted laser desorption/ ionization time of fl ight mass spectrometry (MALDI-TOF MS). The position of the pyridyl groups in the monomer infl uences the degree of quaternization and the extent of conjugation of CPEs. Monomers with 4-pyridyl groups provide CPEs with a low extent of quaternization [N + /(N + + N) = 0.27-0.34] and high extent of conjugation. On the other hand, the CPEs derived from 2-pyridyl-containing monomers are highly quaternized [N + /(N + + N) = 0.77-1.00], however, possess lower conjugation of the main chains. The mechanism assuming quaternization and polymerization as competitive reactions is proposed to explain the difference in the extent of quaternization of CPEs. Prepared CPEs i) are well soluble in polar solvents, e.g., water, methanol, dimethyl sulfoxide, and dimethylformamide, ii) exhibit photoluminescence (emission in the violet to yellow region), and iii) possess high thermal stability. materials with a wide variety of applications, [1][2][3][4][5][6][7][8] including light-emitting diodes (LEDs), [ 9 ] light-emitting electrochemical cells (LECs), [ 10 ] plastic lasers, [ 11 ] solar cells, [ 12 ] fi eld-effect transistors (FETs) [ 13 ] and porous materials. [ 14,15 ] The π-conjugated polyelectrolytes (CPEs) represent a special subclass of CPs. [ 16 ] The CPE polymers comprise π-conjugated main chains and ionic and/or ionizable groups. Unlike the majority of neutral CPs, CPEs additionally exhibit i) solubility in polar solvents as water, aqueous solutions, alcohols, and others environmentally friendly solvents, [17][18][19] ii) amphiphilic nature, which gives CPE macromolecules capability of self-assembling in solutions and ability to interact specifi cally with particular species under measurable optical and/or electrical responses, and iii) simultaneous electronic and ionic conductivity [ 20 ] reducing the electron-injection barrier Emission spectra 400 450 500 550 600 650 Wavelength (nm) Br N N N N N N N N N N Br Br Br Br Br NO CATALYST poly(4PD)
