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Abstract
We report the synthesis and characterization of a novel class of hybrid inorganic–organic building blocks based on polyhedral oligomeric silsesquioxane (POSS) functionalized with 1-haloacetylene moieties (Cl, Br, I). These compounds undergo unprecedented catalyst-free solid-state thermal polymerization, yielding robust, highly crosslinked poly(1-haloacetylene) networks with excellent thermal stability and semiconducting properties. The resulting polymers, polyPOSS-C2Cl, polyPOSS-C2Br, and polyPOSS-C2I, exhibited optical direct band gaps of 2.79, 2.74, and 2.38 eV, respectively. Structural analyses using solid-state NMR, DRIFT, Raman, and PXRD confirmed the successful polymerization and preservation of POSS cage integrity. Kinetic studies revealed pseudo-second-order behavior, with activation energies ranging from 179 to 217 kJ/mol. The materials demonstrated complete insolubility in common solvents and resistance to thermal degradation up to 309 °C, marking them as promising candidates for high-performance optoelectronic applications.
Supplementary materials
Title
supporting information
Description
Supplementary Information contains: : materials, structures of POSS ligands, characterization methods, syntheses, description of experiments. 1H, 13C, 29Si NMR in solution, 13C, 15N, 29Si CP-MAS, uv-vis spectra in solution and in solid state, MALDI, DRIFT and Raman spectra, SEM images, EDS, EDS-mapping, PXRD, Tauc’s plots, TG-DTA data, DSC curves, GC-MS.
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