<i>cis</i> and <i>trans</i> Forms of Near-Infrared Diazaborepin Frameworks with Two Tetracoordinate Boron Atoms

π-Conjugated frameworks <i>cis</i><b>-BN2h</b> with two diazaborepin moieties and <i>trans</i><b>-BN2h1</b> with only one diazaborepin moiety were synthesized via borylation followed by the Scholl reaction. The <i>cis</i> and <i>trans</i> configurations of the substituent on two tetracoordinate boron atoms were controlled by adjusting the reaction solvent, temperature, and concentration. Both molecules exhibit broad absorption across the visible-near-infrared region up to 722 nm. The diazaborepin core is found to enhance electron delocalization and σ-π hyperconjugation, which increase the HOMO energy with a smaller optical bandgap.