Soldatova Natalia S, Radzhabov Amirbek D, Ivanov Daniil M, Burguera Sergi, Frontera Antonio, Abramov Pavel A, Postnikov Pavel S, Kukushkin Vadim Yu
Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University Tomsk 634050 Russian Federation
Institute of Chemistry, Saint Petersburg State University Universitetskaya Nab. 7/9 Saint Petersburg 199034 Russian Federation
Chem Sci. 2024 Jun 24;15(31):12459-12472. doi: 10.1039/d4sc01695e. eCollection 2024 Aug 7.
The structure-directing "key-to-lock" interaction of double σ-(I)-hole donating iodonium cations with the O-flanked pseudo-lacune rims of [β-MoO] gives halogen-bonded iodonium-beta-octamolybate supramolecular associates. In the occurrence of their tetragonal pyramidal motifs, deep and broad σ-(I)-holes of a cation recognize the molybdate backbone, which provides an electronic pool localized around the two lacunae. The halogen-bonded I⋯O linkages in the structures were thoroughly studied computationally and classified as two-center, three-center bifurcated, and unconventional "orthogonal" I⋯O halogen bonds. In the latter, the O-atom approaches orthogonally the C-I-C plane of an iodonium cation and this geometry diverge from the IUPAC criteria for the identification of the halogen bond.
双σ-(I)-空穴供体碘鎓阳离子与[β-MoO]的O侧伪空穴边缘之间的结构导向“钥匙-锁”相互作用产生了卤键合的碘鎓-β-八钼酸盐超分子缔合体。在其四方锥 motif 出现时，阳离子的深而宽的σ-(I)-空穴识别钼酸根主链，该主链提供了围绕两个空穴定位的电子池。对结构中的卤键合I⋯O键进行了全面的计算研究，并将其分类为双中心、三中心分叉和非常规的“正交”I⋯O卤键。在后者中，O原子垂直于碘鎓阳离子的C-I-C平面接近，这种几何结构与IUPAC识别卤键的标准不同。
