Design, Synthesis and Hydrogen Bonding of B₃N₆‐[4]Triangulene

Abstract

Replacement of the allylic C=C−C unit with a N−B−N unit at each of the three zigzag edges of [4]triangulene gives rise to B3N6‐[4]triangulene, which is envisioned to represent a key structural unit of a new hypothetical boron carbon nitride (BC4N). A tert‐butylated B3N6‐[4]triangulene has been successfully synthesized by three‐fold nitrogen‐directed borylation, and the X‐ray crystallographic analysis indicates that its slightly bent triangular polycyclic framework can be viewed as a 1,3,5‐triphenylbenzene connected by three 4π‐electron N−B−N units. The HN−B−NH moiety provides a dual hydrogen‐bond donor, which forms H‐bonds with halide or carboxylate anions in solution, and form DD‐AA hydrogen‐bond arrays with 2,7‐di(tert‐butyl)‐pyrene‐4,5,9,10‐tetraone in the co‐crystal. Moreover, the blue fluorescence of B3N6‐[4]triangulene in solution is responsive to binding p‐nitrobenzoate anion through hydrogen bonds.

Spin engineering of triangulenes and application for nano nonlinear optical materials design

“…Intended heteroatom doping is an important means for improving the NLO response of carbon-based nanomaterials and shedding light on their promising applications, such as organic field-effect transistors, 79 semiconductors, 80 electromagnetics, 81 photocatalysts for water splitting 82 and the next generation of organic spintronic materials. 7 The recent successful syntheses of BNB-or NBN-doped traiangulenes, [83][84][85] [7]triangulene quantum rings, 86 [7]triangulene 87 and the advance in graphene nanosheets and nanoribbons syntheses 88 certainly warrant future syntheses and applications of those proposed triangulenes in nano nonlinear optics.…”

“…The recent successful syntheses of BNB- or NBN-doped traiangulenes, 83–85 [7]triangulene quantum rings, 86 [7]triangulene 87 and the advance in graphene nanosheets and nanoribbons syntheses 88 certainly warrant future syntheses and applications of those proposed triangulenes in nano nonlinear optics.…”

Access to tetracoordinate boron-doped polycyclic aromatic hydrocarbons with delayed fluorescence and aggregation-induced emission under mild conditions

“…38,39 The location of the BN unit was found to be important for the optoelectronic properties because whether the BN unit could fully conjugate with PAHs is highly dependent on its locations. [40][41][42][43][44] Although both the number of BN units [45][46][47][48][49][50] and different orientations of BN units 6,[51][52][53][54] are believed to exhibit non-negligible impact on the optoelectronic properties and intermolecular interactions, only a few of examples have been documented due to the limited synthetic methodology.…”

Design, Synthesis and Hydrogen Bonding of B3N6‐[4]Triangulene

“…Single crystals of 1•(CH 3 CN) 2 were grown by slow diffusion of acetonitrile vapor into its solution in chloroform. X-ray crystallographic analysis [39] revealed an orthorhombic unit cell with an R factor of 7.51 %. In this crystal, 1 has a slightly bent triangular polycyclic framework as shown in Figure 2 a with dihedral angles of 5.6-5.88 between one peripheral benzenoid ring (ring C in Figure 2 a) and the central benzenoid ring (ring A in Figure 2 a).…”

“…Black plate co-crystals of 1 and 6 were obtained by slow diffusion of acetonitrile into a mixed solution of 1 and 6 in THF, while other TDHBAs failed in forming co-crystals with 1. X-ray crystallographic analysis reveals the co-crystal has a composition of 1•(6) 2 •(CH 3 CN) 2 •(THF) 2 and a tetragonal unit cell, [39] where the polycyclic framework of 1 is essentially flat. The bond lengths in the polycyclic framework of 1 in this cocrystal are similar to those found in the crystal of 1•(CH 3 CN) 2 (Figure S2a in the Supporting Information) although the larger R factor (12.37 %) may not allow analysis of the structure of 1 in the co-crystal with high accuracy.…”