Synthesis and Properties of Boron-Containing Heteromerous Bistricyclic Aromatic Enes: Structural Effects on Thermodynamic Stability and Photoreactivity.

Abstract

Overcrowded bistricyclic aromatic enes (BAEs) have several conformations such as twisted and anti-folded conformers, and their stereochemistry and chromism have been studied in earnest. In this study, boron-containing heteromerous BAEs having various tricyclic structures were synthesized and their photophysical properties investigated. Single-crystal X-ray analysis revealed that the introduction of a rigid fluorene unit resulted in a twisted conformer, whereas the introduction of flexible units such as thioxanthene and 9,9-dimethyl-9,10-dihydroanthracene units resulted in an anti-folded conformer. The absorption spectra of the heteromerous BAEs were dependent on the introduced tricyclic structures, suggesting the immense impact of the tricyclic structures on the electronic structures of BAEs. DFT calculations revealed the large effect of the flexibility of the tricyclic structures on the thermodynamic stability of the conformers. In addition, the boron-containing heteromerous BAEs underwent photocyclization reactions, indicating their potential application as precursors of polyaromatic hydrocarbons and helical aromatic materials.