Ligand-free manganese-catalyzed homocoupling of arenes or aryl halides can be carried out under aerobic conditions via the in situ formation of the corresponding aryllithiums. A wide range of biaryls and derivatives has been obtained and a mechanism involving monomeric manganese-oxo complexes has been proposed on the basis of DFT calculations.

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 redshifts 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 % F 4 TCNQ, suggesting potential as p-type doped organic/inorganic semiconductors.