Photochemical Radical Pathways of a Methyl-Substituted Thioxanthone Disulfide Photoinitiator Enabling Oxygen-Tolerant Photopolymerization and In Situ Gold Nanocomposites


ÖZÇELİK KAZANCIOĞLU E., Mumtaz T., Koyuncu U., ARSU N.

Journal of Polymer Science, 2026 (SCI-Expanded, Scopus) identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Basım Tarihi: 2026
  • Doi Numarası: 10.1002/pola.70188
  • Dergi Adı: Journal of Polymer Science
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Anahtar Kelimeler: dynamic disulfide bonds, gold nanoparticles, in situ nanoparticle formation, nanocomposites, photopolymerization, thioxanthone-based photoinitiator
  • Yıldız Teknik Üniversitesi Adresli: Evet

Özet

The photophysical and photochemical performance of a visible-light-active disulfide-based photoinitiator, 4,4′-disulfanediylbis(1-methyl-9H-thioxanthen-9-one) [CH3-TX-S-]2, was investigated and photopolymerization of mono and diacrylate and simultaneous metal nanoparticle generation were reported. The photoinitiator exhibits strong absorption in the visible region with a molar absorptivity of ε = 14,450 L·mol−1·cm−1 at 380 nm, enabling efficient excitation under light irradiation. Steady-state fluorescence measurements revealed a low fluorescence quantum yield (Φf = 0.018), indicating efficient intersystem crossing, which is further supported by phosphorescence emission recorded at 77 K with a lifetime of τp = 63 ms. The triplet energy level was determined as ET = 264 kJ.mol−1, confirming the suitability of the excited triplet state for radical generation and photochemical reduction processes. Real-time FTIR study demonstrated rapid and efficient photopolymerization of diacrylate formulations, with double-bond conversion percentage values reaching 60 within 600 s. Cyclic voltammetry measurements revealed an irreversible oxidation process (Ep,a ≈ 1.76 V) and, together with photophysical data, indicated a strongly reducing excited state, supporting its role in photoinduced electron transfer processes. In parallel, the photogenerated thiyl radicals act as strong photoreductants, enabling the in situ reduction of Au3+ ions to metallic Au0 and the formation of gold nanoparticles during the photopolymerization process.