Biradicaloid Behavior of a Twisted Double Bond.

Abstract

A compound with a highly twisted C═C bond in the intermediate bond dissociation region was isolated, and its biradicaloid nature was experimentally demonstrated. A bianthrone derivative substituted with long-chain alkoxy groups was synthesized, and its twisted conformer was assembled into crystals through hydrophobic intermolecular interactions of the introduced alkoxy chains. X-ray crystallography revealed that the C═C bond connecting the two anthrone rings has a long bond length (1.429 Å) and a large torsional angle (57.33°). In addition, ESR studies revealed that the twisted bianthrone has biradicaloid character with a small singlet-triplet energy gap of 23.8 kJ mol-1. The thermally excited triplet species were observed in the ESR spectrum as distinct fine structures along with a ΔMS = ±2 forbidden transition.