Mechanism of Photoinduced Step Polymerization of Thiophene by Onium Salts:  Reactions of Phenyliodinium and Diphenylsulfinium Radical Cations with Thiophene

Laser flash photolysis and EPR studies were performed to elucidate the mechanism of photoinduced step polymerization of thiophene by using diphenyliodonium (Ph 2 I + ) and triphenylsulphonium (Ph 3 S + ) ions as photoinitiators. Photoexcitation of these ions generated phenyliodinium (PhI •+ ) and diphenylsulphinium (Ph 2 S •+ ) radical cations, which were readily quenched by thiophene with rate constants of k q = 1.26 × 10 10 and 1.7 × 10 5 M -1 s -1, respectively. The transient absorption spectra of the corresponding thiophene radical cations were not directly detectable because of the spectral overlap with the precursor salts. However, the related electron-transfer reaction was confirmed by quenching of the PhI •+ radical cation with bithiophene to form the radical cation of bithiophene, which absorb strongly at 420 nm. EPR studies also confirmed the proposed electron-transfer mechanism through the direct detection of the radical cation of thiophene.