Facile control of system-bath interactions and the formation of crystalline phases of poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(9,9-di-{5′-pentanyl}-fluorenyl-2,7-diyl)] in silicone-based polymer hosts

► Fluorescent silicone-polyfluorene hybrids have been synthesized. ► Polyfluorene chain conformations were analyzed by photoluminescence measurements. ► A detailed PL Franck-Condon analysis were performed of the polyfluorene phases. ► Disordered chains were observed for lower silicone crosslinked yields. ► Polyfluorene α-crystalline phase was observed for higher silicone crosslinked yields.