Triphenylene Analogues with B2N2C2 Cores: Synthesis, Structure, Redox Behavior, and Photophysical Properties

Abstract

A series of alkyl (1-3), aryl (6), and benzo-annulated (4, 5) heteroaromatic triphenylene analogues with B(2)N(2)C(2) cores have been synthesized via chelation of pyridazine derivatives using difunctional Lewis acidic diborabiphenyl precursors. In contrast to triphenylene, NICS(1) calculations on 1 suggested high aromaticities for the central (-11.3 ppm) and outer borabenzene rings (-7.7 ppm), along with nonaromatic behavior for the pyridazine ring (-0.7 ppm). Crystal structure analyses supported this analysis. When the a- and c-faces of the pyridazine moiety were free of substitution (1, 3), planar structures resulted, but upon substitution, a twisted B(2)N(2)C(2) core was observed due to steric repulsion of neighboring hydrogen atoms (e.g., 5). The increase of steric bulk from H (1) to (i)Pr (3) in the planar species was found to result in a dimeric, head-to-tail herringbone packing motif, held together by close intermolecular B...N interactions of 3.39 Angstrom. One-electron reduction by Cp(2)Co was found to afford the radical anions of 3 and 5, which were characterized by broad, featureless singlets in the EPR spectra; [3](.)(-)[Cp(2)Co](+) was characterized by X-ray crystallography. While the planar structures (1-4) were observed to possess weak fluorescence (Phi(F) = 0.02-0.08) with either yellow-orange (ca. 555 nm) or green emission (521 nm), the twisted structures (5, 6) were found to be nonfluorescent.