Department of Chemistry, Merkert Chemistry Center , Boston College, Chestnut Hill, Massachusetts 02467, United States.
Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux, UMR CNRS 5254, Université de Pau et des Pays de l'Adour, Pau, France.
J Am Chem Soc. 2017 May 3;139(17):6082-6085. doi: 10.1021/jacs.7b02661. Epub 2017 Apr 24.
The least stable isomer of the parental BN naphthalene series has been synthesized in a simple four-step sequence. Its experimental electronic structure characterization via UV-PES, cyclic voltammetry, and UV-vis spectroscopy in direct comparison with three other known BN naphthalene isomers has established two guiding principles for predicting the electronic structures of BN acene compounds: (1) Orientational BN isomers have similar HOMO-LUMO gaps. (2) For each pair of orientational BN isomers, the more thermodynamically stable compound has the lower HOMO energy. Furthermore, we demonstrate that BN/CC isosterism in the context of BN-9,1-Naph can impact crystal packing to favor a cofacial π-stack motif.
已通过简单的四步序列合成了 BN 萘系列中最不稳定的异构体。通过与其他三种已知 BN 萘异构体进行直接比较的 UV-PES、循环伏安法和 UV-vis 光谱学对其进行了实验电子结构表征，为预测 BN 并五苯化合物的电子结构建立了两个指导原则：(1) 取向 BN 异构体具有相似的 HOMO-LUMO 能隙。(2) 对于每一对取向 BN 异构体，热力学稳定性更高的化合物具有更低的 HOMO 能量。此外，我们证明了 BN-9,1-Naph 中 BN/CC 等排体可影响晶体堆积，有利于共面 π-堆叠基序。
