Key-to-lock halogen bond-based tetragonal pyramidal association of iodonium cations with the lacune rims of beta-octamolybdate

The structure-directing "key-to-lock" interaction of double σ-(I III )-hole donating iodonium cations with the O-flanked pseudo-lacune rims of [β-Mo 8 O 26 ] 4− gives halogen-bonded iodonium-beta-octamolybate supramolecular associates. In the occurrence of their tetragonal pyramidal motifs...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2024-08, Vol.15 (31), p.12459-12472
Main Authors: Soldatova, Natalia S, Radzhabov, Amirbek D, Ivanov, Daniil M, Burguera, Sergi, Frontera, Antonio, Abramov, Pavel A, Postnikov, Pavel S, Kukushkin, Vadim Yu
Format: Article
Language:English
Subjects:
Cations
Chemistry
Rims
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Summary:The structure-directing "key-to-lock" interaction of double σ-(I III )-hole donating iodonium cations with the O-flanked pseudo-lacune rims of [β-Mo 8 O 26 ] 4− gives halogen-bonded iodonium-beta-octamolybate supramolecular associates. In the occurrence of their tetragonal pyramidal motifs, deep and broad σ-(I III )-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 III -C plane of an iodonium cation and this geometry diverge from the IUPAC criteria for the identification of the halogen bond. Iodonium cations recognize the molybdate backbone furnishing "key-to-lock" halogen-bonded supramolecular associates.
ISSN:2041-6520
2041-6539
DOI:10.1039/d4sc01695e