Captodative Effect Facilitates the Excitation in Diboron Molecule (CAAC)₂B₂(SH)₂

Given the extraordinary versatility in chemical reactions and applications, boron compounds have gained increasing attentions in the past two decades. One of the remarkable advances is the unprecedented preparation of unsaturated boron species. Notably, Braunschweig et al. found that the cyclic (alkyl)(amino) carbenes (CAACs) stabilized diboron molecules (CAAC) 2 B 2 (SR) 2 host unpaired electrons and exist in the 90°‐twisted diradical form, while other analogues, such as N‐heterocyclic carbenes (NHCs), stabilized diboron molecules prefer a conventional B=B double bond. Since previous studies recognized the differences in the steric effect between CAAC and NHC carbenes, here we focused on the role of thiol substituents in (CAAC) 2 B 2 (SR) 2 by gradually localizing involved electrons. The co‐planarity of the thiol groups and the consequent captodative effect were found to be the culprit for the 90°‐twisted diradical form of (CAAC) 2 B 2 (SR) 2 . Computational analyses identified two forces contributing to the π electron movements. One is the “push” effect of lone pairs on the sulfur atoms which boosts the π electron delocalization between the BB center and CAACs. The other is the π electron delocalization within each (CAAC)B(SR) fragment where the pull effect originates from the π electron withdrawal by CAACs. There are two such independent and orthogonal push‐pull channels which function mainly in individual (CAAC)B(SR) fragments. This enhanced π push‐pull effect in the triplet state facilitates the electronic excitation in (CAAC) 2 B 2 (SR) 2 by reducing the singlet‐triplet gap.