Description:
<jats:title>Abstract</jats:title><jats:p>Using 4‐phenylpyridine or 2‐phenylpyridine in place of biphenyl, two electron‐poor phenylpyridyl‐fused boroles, <jats:bold>[TipPBB1]<jats:sub>4</jats:sub></jats:bold> and <jats:bold>TipPBB2</jats:bold> were prepared. <jats:bold>[TipPBB1]<jats:sub>4</jats:sub></jats:bold> adopts a unique coordination mode and forms a tetramer with a cavity in both the solid state and solution. The boron center of <jats:bold>TipPBB2</jats:bold> is 4‐coordinate in the solid state but the system dissociates in solution, leading to 3‐coordinate borole species. Compared to its borafluorene analogues, the electron‐accepting ability of <jats:bold>TipPBB2</jats:bold> is largely enhanced by the pyridyl group. <jats:bold>TipPBB2</jats:bold> exhibits dual fluorescence in solution due to an equilibrium between free <jats:bold>TipPBB2</jats:bold> and a weak intermolecular coordination adduct with a second molecule. This equilibrium was further investigated by low‐temperature NMR spectroscopy and photophysical studies. Theoretical studies indicate that the highest occupied molecular orbital (HOMO) of <jats:bold>TipPBB2</jats:bold> localizes at the Tip group, in contrast to its borafluorene derivatives, wherein the HOMOs are localized on the borafluorene cores.</jats:p>