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

Author:

Scholz Alexander S.1,Massoth Julian G.1,Stoess Lennart1,Bolte Michael1ORCID,Braun Markus2ORCID,Lerner Hans‐Wolfram1ORCID,Mewes Jan‐M.3ORCID,Wagner Matthias1ORCID,Froitzheim Thomas3ORCID

Affiliation:

1. Institut für Anorganische und Analytische Chemie Goethe-Universität Frankfurt am Main Max-von-Laue-Straße 7 60438 Frankfurt am Main Germany

2. Institut für Physikalische und Theoretische Chemie Goethe-Universität Frankfurt am Main Max-von-Laue-Straße 7 60438 Frankfurt am Main Germany

3. Mulliken Center for Theoretical Chemistry Institut für Physikalische und Theoretische Chemie Rheinische Friedrich Wilhelms-Universität Bonn Beringstr. 4 53115 Bonn Germany

Abstract

AbstractNBN‐ 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 14 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.

Publisher

Wiley

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