Oxygen-sensing properties of 5, 10, 15, 20-tetraphenylporphinato platinum(II) and palladium(II) covalently bound on poly(isobutyl-co-2,2,2-trifluoroethyl methacrylate)

Makoto Obata, Noriko Matsuura, Kazunori Mitsuo, Hiroki Nagai, Keisuke Asai, Masafumi Harada, Shiho Hirohara, Masao Tanihara, Shigenobu Yano

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22 Citations (Scopus)

Abstract

A novel methacrylate monomer bearing 5, 10, 15, 20tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2-trifluoroethyl methacrylate (TFEM) to give poly (IBM-co-TFEM) bearing PdTPP (copolymer 2a) as a dye-conjugated oxygen-permeable polymer for pressure-sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV-vis spectroscopy and extended X-ray absorption fine structure analysis. The Stern-Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM-co-TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b) previously reported. The plots were successfully fitted with a two-site model to give two distinct Stern-Volmer constants (Ksv1 andKsv2 and the partition ratio f1. Interestingly, the f1 values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM-co-TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature-dependent and the other temperature-independent, in the mixture of PdTPP and poly(IBM-co-TFEM). The dye-conjugation approach effectively eliminates the temperature-dependent, but not the temperature-independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature-dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature-independent one appears to be inherent nature in PdTPP.

Original languageEnglish
Pages (from-to)663-670
Number of pages8
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume48
Issue number3
DOIs
Publication statusPublished - 2010 Feb 1

Keywords

  • Luminescence
  • Metalloporphyrin
  • Oxygen-sensing
  • Photochemistry
  • Pressure-sensitive paint
  • Radical polymerization
  • Sensors

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

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