Formation of color centers and paramagnetic species by alkaline hydrolysis of polydiphenylenesulfophthalide |
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Authors: | N M Shishlov V N Khrustaleva Sh S Akhmetzyanov K Yu Murinov N L Asfandiarov A N Lachinov |
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Institution: | (1) Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054 Ufa, Russian Federation;(2) Institute of Molecular and Crystalline Physics, Ufa Research Center for the Russian Academy of Sciences, 151 prosp. Oktyabrya, 450075 Ufa, Russian Federation |
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Abstract: | Blue color centers (CC) (an intense absorption band (AB) at 566 nm and a weaker AB at 350 nm) and paramagnetic species (PMS)
that give an ESR singlet withg=2.0028 and δH=10 Oe are formed by the treatment of a DMSO solution of polydiphenylenesulfophthalide with an excess of LiOH. The formation
of blue CC is accompanied by a decrease in the intensity of the absorption band of the phenyl groups of the polymer at 270
nm. The blue CC were attributed to quinoid structures like the Chichibabin hydrocarbon. The long-wave absorption at 650–800
nm was assigned to the regions of quinoid-benzoid conjugation. The color centers and PMS were also observed when the polymer
was hydrolyzed in cyclohexanone; however, in this case, the reaction was accompanied by polymer aggregation. The electronic
spectrum of the Chichibabin hydrocarbon was calculated by the PM3 method. The identity of CC formed by alkaline hydrolysis
and appearing in the polymer—aniline—cyclohexanone system was shown. The absence of “quinoid” CC for polyterphenyl sulfophthalide
was explained by the energetically unfavorable singlet state for structures similar to the Müller hydrocarbon.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 2, pp. 295–300, February, 2000. |
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Keywords: | polyarylenesulfophthalides alkaline hydrolysis triarylmethyl radicals the Chichibabin hydrocarbon the Müller hydrocarbon electronic spectra ESR spectra |
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