NBN‐ and BNB‐Phenalenyls: the Yin and Yang of Heteroatom‐doped π Systems

The photophysical properties of NBN-phenalenyls are experimentally and quantum-chemically investigated, shedding light on the substituent-dependent emission characteristics of these compounds. Co-aggregation of a suitable NBN- with its complementary BNB-phenalenyl in a microsuspension leads to a drastic red-shift in emission wavelength compared to the emission of an equimolar mixture in solution.

Abstract

NBN- and BNB-doped phenalenyls are isoelectronic to phenalenyl anions and cations, respectively. They represent a pair of complementary molecules that have essentially identical structures but opposite properties as electron donors and acceptors. The NBN-phenalenyls 1–4 considered here were prepared from N,N’-dimethyl-1,8-diaminonaphthalene and readily available boron-containing building blocks (i. e., BH₃⋅SMe₂ (1), p-CF₃-C₆H₄B(OH)₂ (2), C₆H₅B(OH)₂ (3), or MesBCl₂/iPr₂NEt (4)). Treatment of 1 with 4-Me₂N-2,6-Me₂-C₆H₂Li gave the corresponding NBN derivative 5. The BNB-phenalenyl 6 was synthesized from 1,8-naphthalenediyl-bridged diborane(6), PhNH₂, and MesMgBr. A computational study reveals that the photoemission of 1, 4, and 5 originates from locally excited (LE) states at the NBN-phenalenyl fragments, while that of 2 is dominated by charge transfer (CT) from the NBN-phenalenyl to the p-CF₃-C₆H₄ fragment. Depending on the dihedral angle θ between its Ph and NBN planes, compound 3 emits mainly from a less polar LE (θ >55°) or more polar CT state (θ <55°). In turn, the energetic preference for either state is governed by the polarity of the solvent used. An equimolar aggregate of the NBN- and BNB-phenalenyls 3 and 6 (in THF/H₂O) shows a distinct red-shifted emission compared to that of the individual components, which originates from an intermolecular CT state.

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