Oxoborane Formation Turns on Formazanate-Based Photoluminescence

Chemistry. 2019 Aug 22;25(47):11015-11019. doi: 10.1002/chem.201902419. Epub 2019 Jul 8.

Abstract

The synthesis of compounds containing multiple bonds to boron has challenged main-group chemists for decades. Despite significant progress, the possibility that the formation of such bonds can turn on photoluminescence has received minimal attention. We report an oxoborane (B=O) complex that is electronically stabilized by a formazanate ligand in the absence of significant steric bulk and, unlike the common BX2 (X=F, Cl) formazanate adducts, exhibits intense photoluminescence. The latter property was rationalized through density-functional calculations which indicated that the B=O bond enhances photoluminescence by drastically reducing differences between the ligand's geometries in the ground and excited states. The title oxoborane compound was synthesized from an air- and moisture-stable BCl2 formazanate complex and subsequently converted to a redox-active boroxine. Each of these species may also serve as a precursor to functional materials.

Keywords: X-ray crystallography; boron multiple bonds; formazanate ligands; oxoboranes; turn-on photoluminescence.