Conjugated Copolymers That Shouldn't Be

Abstract

Multiple studies have explored using cage silsesquioxanes (SQs) as backbone elements in hybrid polymers motivated by their well-defined structures and physical and mechanical properties. As part of this general exploration, we report unexpected photophysical properties of copolymers derived from divinyl double decker (DD) SQs, [vinyl(Me)Si(O_0.5 )₂ ][PhSiO_1.5 ]₈ [(O_0.5 )₂ Si(Me)vinyl] (vinylDDvinyl). These copolymers exhibit strong emission red-shifts relative to model compounds, implying unconventional conjugation, despite vinyl(Me)Si(O-)₂ siloxane bridges. In an effort to identify minimum SQ structures that do/do not offer extended conjugation, we explored Heck catalyzed co-polymerization of vinyl-ladder(LL)-vinyl compounds, vinyl(Me/Ph)Si(O_0.5 )₂ [PhSiO_1.5 ]₄ (O_0.5 )₂ Si(Me/Ph)vinyl, with Br-Ar-Br. Most surprising, the resulting oligomers show 30-60 nm emission red-shifts beyond those seen with vinylDDvinyl analogs despite lacking a true cage. Further evidence for unconventional conjugation includes apparent integer charge transfer (ICT) between LL-co-thiophene, bithiophene, and thienothiophene with 10 mol % F₄ TCNQ, suggesting potential as p-type doped organic/inorganic semiconductors.