Electronic Push-Pull Modulation by Peripheral Substituents in Pentaaryl Boroles.

Establishing access to a bulky tetraaryl dilithiobutadiene (Ph*C)4 Li2 (Ph*=3,5-tBu2 (C6 H3 )) allowed for the synthesis of five-membered heterocycles with incorporated main-group elements. Along with an amino borole, a set of substituted pentaaryl boroles (Ph*C)4 BAr has been synthesized. The examination of their absorption spectra and computational studies by means of DFT granted insight into the influence of peripheral substituents on the electronic features of the parent pentaphenyl borole (PhC)4 BPh. Introduction of the more electron-rich Ph* residue at the carbon atoms increases the HOMO energy, redshifting the visible π/π*-absorption bands compared with the parent pentaphenyl borole. The influence on the frontier orbitals of three different boron-bound aryls with electronically modulating substituents in the remote 3,5-positions Ar=3,5-R2 -C6 H3 (R=Me, H, CF3 ) was studied. The substituents were found to increase (+I effect, Me) or decrease (-I effect, CF3 ) the LUMO energy, thus directly affecting the visible absorption spectra. This represents the first study on HOMO-LUMO-gap adjustments by a combined push-pull approach of a substituted pentaphenylborole.