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One-pot multiple borylation of phenylhydrazones to a series of novel boron–nitrogen analogues of benzopentalene by the cleavage of C–H bonds with PhBBr2 mediated by NEt3 has been established. The resulting BN benzopentalenes feature unique electronic structures and are luminescent both in solution and the solid state.

Graphical abstract: Multiple C–H borylation of phenylhydrazones to boron–nitrogen analogues of benzopentalene

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