Polyarylboranes are a new class of organic-inorganic hybrid nano-molecular ions derived from the substitution chemistry between polyhedral boranes and aromatic hydrocarbons. The ten and twelve vertex polyhedral borane clusters exhibit remarkably high thermal stability and resistance to oxidative degradation. The stability of these boron clusters is owing to the extensive delocalization of their framework bonding electrons, giving rise to three-dimensional aromaticity. The substitution chemistry of polyhedral boron clusters with aromatic ligands was previously limited in scope. However, we recently reported this extensive polysubstitution chemistry of polyhedral borane anions such as closo - decaborate [B10H10]2- and closo-dodecaborate [B12H12]2-, where up to ten of the B-H vertices may be replaced with a wide range of different aryl ligands through stable boron-carbon bonds resulting in polyarylboranes. Many of these pseudospherical anions possess ligand size-dependent diameters ranging between 1.3 – 3.5 nanometers which exhibit interesting photophysical properties, including high solution-phase fluorescence quantum yields, high molar absorptivities and extraordinarily large stoke shifts. Furthermore, the fluorescence emission, excitation and absorption spectra for most of these products change reversibly upon applying specific electrochemical potentials, thus exhibiting redox-controlled fluorescence switching and electrochromism. The properties of each product depends upon the composition and the structure of the bound ligands and these may be tailored through chemical modification of the surface. The syntheses, structural characterization, electronic and spectroscopic properties will be described during the presentation.

Polyarylated nano-molecular boron clusters exhibiting redox-controlled fluorescence switching and electrochromism

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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