Since the discovery of the icosahedral dodecahydrododecaborate dianion nearly sixty years ago, extensive cage substitution chemistry has been developed; albeit the degree of substitution is typically limited to placing one or two substituents per cage.  To date, reports of polysubstitution (n&gt;3) of dodecahydrododecaborate have been limited to substitution with halogen, methyl, or hydroxyl (or its derivatives).  Previous examples of cage substitution with aryl moieties are extremely limited and minimal in scope (n&lt;3).<br/>Here, the author reports new, extensive, and extremely facile polyaryl-substitution chemistry of dodecahydrododecaborate.  Substitution of between one and ten of the B-H vertices with phenyl, substituted phenyl, or polycyclic aromatic moieties produces small, nearly spherical ions which range in diameter between 1.5 to greater than 2 nanometers.  In each example, these polyarylboranes exhibit unique spectroscopic properties, including tailorable fluorescence emission.  The florescence quantum yields for several of these new species have been measured and are quite high (ΦF &gt;0.5).  In each example, ΦF is much higher than those of the free substituents and the electronic spectra are significantly different, suggesting a high degree of conjugation between the aryl substituents and the polyhedral borane core.<br/>

Polyarylboranes: A new and diverse class of small, metal-free quantum dots exhibiting high fluorescence quantum yields

251st National Meeting (2016)

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