Cui Peng-Fei, Liu Xin-Ran, Jin Guo-Xin
State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200433, People's Republic of China.
J Am Chem Soc. 2023 Sep 13;145(36):19440-19457. doi: 10.1021/jacs.3c05563. Epub 2023 Aug 29.
The utilization of carboranes in supramolecular chemistry has attracted considerable attention. The unique spatial configuration and weak interaction forces of carboranes can help to explore the properties of supramolecular complexes, particularly via host-guest chemistry. Additionally, certain difficulties encountered in carborane development─such as controlled B-H bond activation─can be overcome by judiciously selecting metal centers and their adjacent ligands. However, few studies are being conducted in this nascent research area. With advances in this field, novel carborane-based supramolecular complexes will likely be prepared, structurally characterized, and intrinsically investigated. To expedite these efforts, we present major findings from recent studies, including π-π interactions, host-guest associations, and steric effects, which have been leveraged to implement a regioselective process for activating B(2,9)-, B(2,8)-, and B(2,7)-H bonds of -carboranes and B(4,7)-H bonds of -carboranes. Future studies should clarify the unique weak interactions of carboranes and their potential for enhancing the utility of supramolecular complexes. Although carboranes exhibit several unique weak interactions (such as dihydrogen-bond [B-H···H-C], B-H···M, and B-H···π interactions), the manner in which they can be utilized remains unclear. Supramolecular complexes, particularly those based on host-guest chemistry, can be utilized as a platform for demonstrating potential applications of these weak interactions. Owing to the importance of alkane separation, applications related to the recognition and separation of alkane isomers via dihydrogen-bond interactions are primarily summarized. Advances in the research of unique weak interactions in carboranes will certainly lead to more possibilities for supramolecular chemistry.
碳硼烷在超分子化学中的应用已引起了相当大的关注。碳硼烷独特的空间构型和弱相互作用力有助于探索超分子配合物的性质，特别是通过主客体化学。此外，通过明智地选择金属中心及其相邻配体，可以克服碳硼烷发展过程中遇到的某些困难，例如可控的B-H键活化。然而，在这个新兴的研究领域中，相关研究较少。随着该领域的进展，新型的基于碳硼烷的超分子配合物可能会被制备、进行结构表征并深入研究其内在性质。为了加快这些研究工作，我们展示了近期研究的主要发现，包括π-π相互作用、主客体缔合和空间效应，这些已被用于实现对-碳硼烷的B(2,9)-、B(2,8)-和B(2,7)-H键以及-碳硼烷的B(4,7)-H键进行区域选择性活化的过程。未来的研究应阐明碳硼烷独特的弱相互作用及其增强超分子配合物实用性的潜力。尽管碳硼烷表现出几种独特的弱相互作用（如双氢键[B-H···H-C]、B-H···M和B-H···π相互作用），但其利用方式仍不明确。超分子配合物，特别是基于主客体化学的配合物，可作为展示这些弱相互作用潜在应用的平台。由于烷烃分离的重要性，主要总结了通过双氢键相互作用识别和分离烷烃异构体的相关应用。碳硼烷独特弱相互作用研究的进展必将为超分子化学带来更多可能性。
