Alternating copolymers of maleimides containing pyrenyl and alkynylpyrenyl moieties with isobutene (IB) were synthesized as a new class of heat‐resistant and fluorescent polymers. N‐(1‐Pyrenyl)maleimide (1) and N‐[4‐(1‐pyrenylethynyl)phenyl]maleimide (2) were copolymerized with IB in the presence and absence of N‐methylmaleimide (3). The obtained maleimide/IB copolymers showed excellent thermal stability and high glass transition temperatures, and were soluble in common organic solvents. The copolymers including the alkynylpyrenyl fluorophore emitted strong fluorescence with a high quantum efficiency (Φ = 0.83) even in the presence of air and upon heating. Solid‐state fluorescence in transparent films was also investigated.magnified image

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