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(Poly)terephthalates with Efficient Blue Emission in the Solid State
Author(s) -
Shimizu Masaki,
Shigitani Ryosuke,
Kinoshita Takumi,
Sakaguchi Hiroshi
Publication year - 2019
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201801619
Subject(s) - fluorescence , polymer , alkoxy group , photochemistry , toluene , terephthaloyl chloride , materials science , methyl methacrylate , alkylation , absorption spectroscopy , copolymer , chemistry , polymer chemistry , organic chemistry , catalysis , alkyl , physics , quantum mechanics
We prepared dimethyl and diaryl 2,5‐dialkoxytere‐phthalates from dimethyl 2,5‐dihydroxyterephthalate in good‐to‐high yields via alkylation or a sequence of alkylation, hydrolysis, chlorination, and condensation. The absorption spectra of the dialkoxyterephthalates contain a small band at 332–355 nm, which could be assigned to intramolecular charge‐transfer transition from the alkoxy to alkoxycarbonyl groups on the basis of theoretical calculations using density functional theory. The dialkoxyterephthalates exhibited blue fluorescence with moderate‐to‐excellent quantum yields not only in solution but also in the solid state, such as a poly(methyl methacrylate) (PMMA) film and a powder. The solid‐state quantum yields of the diisopropoxy‐substituted terephthalates were similar or considerably higher than those of the dimethoxy‐substituted counterparts. Copolymerization of 2,5‐diisopropoxyterephthaloyl chloride and 1,4‐butanediol with or without terephthaloyl chloride gave brilliantly blue fluorescent polymers, whose quantum yields were 0.72 and 0.71 in toluene and 0.46 and 0.40 in the neat film, respectively. Furthermore, white emission was achieved when a fluorescent yellow 2,5‐diaminoterephthalate was doped into the thin film of the blue fluorescent polymer at 0.4 wt %.