Nonalternant B,N-Embedded Helical Nanographenes Containing Azepines: Programmable Synthesis, Responsive Chiroptical Properties and Spontaneous Resolution into a Single-Handed Helix

Abstract

Heteroatom-embedded helical nanographenes (NGs) constitute an important and appealing class of intrinsically chiral materials. In this work, a series of B,N-embedded helical NGs (BN-HNGs) bearing azepines was synthesized via stepwise regioselective cyclodehydrogenation. First, the phenyl- or nitrogen-bridged dimers were efficiently clipped into highly congested model compounds 1 and 2. Later, the controllable Scholl reactions of the tetraphenyl-tethered precursor generated 1, 7 or 8 new C−C bonds, thereby establishing a robust method for the preparation of nonalternant BN-HNGs with up to 31 fused rings. The helical bilayer nature was unambiguously verified by X-ray diffraction analysis. The helical chirality was transferred to the stereogenic boron centers upon fluoride coordination, with a concave-concave structure to comply with the bilayer skeleton. Notably, the largest nonalternant BN-HNG (6) spontaneously resolved into a homochiral 41 helix structure as a molecular spiral staircase during crystallization via conglomerate formation at the single-crystal scale. The large twisted C2-symmetric π-surface and the dynamic chiral skeleton induced by curved azepines might have synergistic effects on self-recognition of enantiomers of 6 to achieve the intriguing spontaneous resolution behavior. The chiroptical properties of the enantiomer of 6 were further investigated, revealing that 6 had a strong chiroptical response in the visible range (400–700 nm).