Synthesis, characterization, and photolysis of poly [3,5-di-tert-butyl-4- [(2,4,6-tri-tert-butylphenyl)oxalato]phenylacetylene], a photochemical polyradical precursor

Journal of Polymer Science, Part A: Polymer Chemistry

Volumn 35, Issue 11, 1997, Pages 2167-2176

  Lahti, Paul M ^a   Inceli, Ahmet Levent ^a   Rossitto, Frank C ^a  

^a UNIVERSITY OF MASSACHUSETTS   (United States)

Author keywords

Magnetism; Molecular magnetism; Polyacetylene; Polyphenylacetylene; Polyradicals

Indexed keywords

CHARACTERIZATION; ELECTRON SPIN RESONANCE SPECTROSCOPY; FERROMAGNETISM; PHOTOLYSIS; POLYACETYLENES; SURFACES; SYNTHESIS (CHEMICAL);

POLYPHENYLACETYLENE; POLYRADICAL;

ORGANIC POLYMERS;

EID: 0031210450     PISSN: 0887624X     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1099-0518(199708)35:11<2167::AID-POLA7>3.0.CO;2-V     Document Type: Article

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35. DPPH is codissolved with polymethylmethacrylate in chloroform at a known wt/wt ratio. The solution is poured carefully into aluminum pans, and the solvent removed to form films containing a known weight percentage of spins based on amount of DPPH. The films show show no change in the UV-vis spectrum of DPPH after 5 years in a nitrogen-flushed bottle at -20°C, and do not decay at an appreciable rate at room temperature in air. Analytically weighed portions of such films provide spin-counting standards for comparison to other solid-state samples by double integration of the ESR signals of standard vs. unknown under any comparable conditions. Fuller details of this spin counting methodology are provided in D. A. Modarelli, Ph. D. Thesis, Univ. of Massachusetts, Amherst, MA (1990) and F. Rossitto, Ph. D., University of Massachusetts, Amherst, MA (1994).
36. Proposed mechanisms for solid-state decay of pendant polyphenoxyl radical sites have been described previously in F. C. Rossitto and P. M. Lahti, J. Polym. Sci., Polym. Chem., 30, 1335 (1992). Even monomeric, simply substituted phenoxyl radicals typically undergo considerable (and sometimes reversible) dimerization in the solid or solution phases: cf. descriptions and numerous references in E. R. Altwicker, Chem. Rev., 67, 475 (1967). Reference 14b describes the postphotolysis reactions of DAOs in the the solid state, so far as we have been able to discern.
37. Proposed mechanisms for solid-state decay of pendant polyphenoxyl radical sites have been described previously in F. C. Rossitto and P. M. Lahti, J. Polym. Sci., Polym. Chem., 30, 1335 (1992). Even monomeric, simply substituted phenoxyl radicals typically undergo considerable (and sometimes reversible) dimerization in the solid or solution phases: cf. descriptions and numerous references in E. R. Altwicker, Chem. Rev., 67, 475 (1967). Reference 14b describes the postphotolysis reactions of DAOs in the the solid state, so far as we have been able to discern.
38. Cf. recent work describing the use of a partially BAPA functionalized poly(1,4-phenylene vinylene) with pendant phenoxyl groups to generate high spin domains within a conjugated polymer in the solid state: M. Takahashi, H. Nishide, E. Tsuchida, and P. M. Lahti, Chem. Mater., 9, (1997).