Moaven Shiva, Watson Brandon T, Polaske Thomas J, Karl Brian M, Unruh Daniel K, Bowling Nathan P, Cozzolino Anthony F
Department of Chemistry and Biochemistry, Texas Tech University, 1204 Boston Avenue, Lubbock, Texas 79409-1061, United States.
Department of Chemistry, University of Wisconsin-Stevens Point, 2101 Fourth Avenue, Stevens Point, Wisconsin 54481, United States.
Inorg Chem. 2021 Aug 2;60(15):11242-11250. doi: 10.1021/acs.inorgchem.1c01232. Epub 2021 Jul 21.
Triple pnictogen bonding refers to the ability of a pnictogen atom to engage in three simultaneous pnictogen bonds (PnBs) to a complementary partner through a single pnictogen atom. This supramolecular strategy was recently introduced as a unique facet of pnictogen bonding as compared to other named supramolecular interactions. Here, the ability of bismuth to participate in this phenomenon is demonstrated using Bi((NCH)CH). The study reveals that Bi engages in stronger PnBs than the analogous Sb system. The results have been contrasted with Bi systems that form strong coordination bonds, and analysis of the electron density along the bond path reveals key differences. The solution behavior of these newly synthesized supramolecules were studied by PFGSE NMR spectroscopy and they are found to remain intact in solution. Molecular design strategies that allow for triple pnictogen bonding should find use in the fields of molecular recognition and crystal engineering.
三重氮族元素键合是指一个氮族元素原子能够通过单个氮族元素原子与一个互补的伙伴同时形成三个氮族元素键（PnBs）。与其他已命名的超分子相互作用相比，这种超分子策略最近作为氮族元素键合的一个独特方面被引入。在这里，使用Bi((NCH)CH)证明了铋参与这种现象的能力。研究表明，铋形成的PnBs比类似的锑体系更强。将这些结果与形成强配位键的铋体系进行了对比，并且沿着键路径的电子密度分析揭示了关键差异。通过脉冲场梯度自旋回波（PFGSE）核磁共振光谱研究了这些新合成的超分子的溶液行为，发现它们在溶液中保持完整。允许形成三重氮族元素键合的分子设计策略应该会在分子识别和晶体工程领域得到应用。
