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High boron content systems were prepared by the peripheral functionalisation of 1,3,5-triphenylbenzene (TPB) and octavinylsilsesquioxane (OVS) with two different anionic boron clusters: closo -dodecaborate (B 12 ) and cobaltabisdicarbollide (COSAN). TPB was successfully decorated with three cluster units by an oxonium ring-opening reaction, while OVS was bonded to eight clusters by catalysed metathesis cross-coupling. The resulting compounds were spectroscopically characterised, and their solution-state photophysical properties analysed. For TPB, the presence of COSAN dramatically quenches the fluorescence emission (λ em = 369 nm; Φ F = 0.8%), while B 12 -substituted TPB shows an appreciable emission efficiency (λ em = 394 nm; Φ F = 12.8%). For octasilsesquioxanes, the presence of either COSAN or B 12 seems to be responsible for ∼80 nm bathochromic shift with respect to the core emission, but both cases show low emission fluorescence (Φ F = 1.4-1.8%). In addition, a remarkable improvement of the thermal stability of OVS was observed after its functionalisation with these boron clusters.

Blue Emitting Star-Shaped and Octasilsesquioxane-Based Polyanions Bearing Boron Clusters. Photophysical and Thermal Properties