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Copolymerization of N ‐(prop‐1‐yne‐3‐yl)‐4‐(piperidine‐1‐yl)‐1,8‐naphthalimide with Arylacetylenes into Fluorescent Polyacetylene‐Type Conjugated Polymers
Author(s) -
Sivkova Radoslava,
Trhlíková Olga,
Zedník Jiří,
Sedláček Jan
Publication year - 2015
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201500240
Subject(s) - polyacetylene , copolymer , fluorescence , polymer chemistry , chemistry , fluorophore , monomer , photochemistry , piperidine , polymerization , polymer , conjugated system , bifunctional , organic chemistry , catalysis , physics , quantum mechanics
N ‐(prop‐1‐yne‐3‐yl)‐4‐(piperidine‐1‐yl)‐1,8‐naphthalimide (PNPr), i.e., the monomer with a terminal ethynyl group and 1,8‐naphthalimide fluorophore, has been successfully copolymerized with a series of monoethynylarenes into well‐soluble high‐molecular‐weight ( M w up to 210 000) linear polyacetylene‐type copolymers containing from 14 to 51 mol% units derived from PNPr. The copolymerization of PNPr with bifunctional 4,4′‐diethynylbiphenyl provides polyacetylene‐type micro/mesoporous fluorescent network containing 8 mol% PNPr units and exhibiting the Brunauer–Emmett–Teller surface of ≈1000 m 2 g −1 . The copolymerizations (catalyzed with acetylacetonato(norborna‐2,5‐diene)rhodium complex, [Rh(nbd)acac]) proceed smoothly despite the fact that the homopolymerization of PNPr fails. The fluorescence of PNPr (emission at ≈ 510 nm) has been retained after the incorporation of PNPr into the copolymers. The fluorescence of the copolymers can be induced by a direct excitation of PNPr units or via an energy transfer mechanism. In the latter case, the comonomeric units with aromatic hydrocarbon fluorophores (e.g., of the biphenyl‐type) emitting at 380–400 nm (after irradiation with 300 nm UV radiation) serve as energy donors for fluorescent PNPr acceptors. The difference between the wavelengths of the primary absorbed radiation and the finally emitted radiation is 210 nm.