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[{AgL}2Mo8O26]n complexes: a combined experimental and theoretical study

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Self-assembly reactions between AgNO3, L (PPh3, PPh2Py, AsPh3, SbPh3) and [β-Mo8O26]4− in DMF led to the formation of [β-{AgL}2Mo8O26]2− anions, which were isolated as Bu4N+ salts (1–4) and characterized by XRD, IR and elemental analysis. In the crystal structures Ag+ can switch the coordination number from 5 (P, As) to 6 (Sb) by uptake of a DMF molecule. High-level QAIM analysis of the coordination sphere around Ag shows critical points even in the case of longer Ag–O distances. Changing the ligand type to a family of substituted pyridines results in novel Ag–L–POM complexes with different environments around Ag+. For 3-X-pyridine ligands (X = Cl, Br, I), complexes with additional DMF molecules [β-{AgL(DMF)}2Mo8O26]2− (5–7) have been isolated. Halogen bonding of the X⋯O type was detected in the crystal structures of 5–7 and studied by DFT calculations, providing estimated energies from 0.9 to 3.4 kcal mol−1. Variation of substituents at the pyridine ring results in the formation of [β-{AgL}2Mo8O26]2− in the case of 2-NH2-py (8), 2-CH3-Py (9), 2,4,6-collidine (10) and 2,6-NH2-py (11). Solution behavior of 1–4 in CH3CN was studied by a hyphenated HPLC–ICP-AES technique. According to the results, the [β-{AgL}2Mo8O26]2− anions are largely dissociated in this medium. An attempt to change the [Mo8O26]4− precursor to [Mo6O19]2− (in the case of AgNO3 and PyPPh2) resulted in the crystallization of [Ag2(PyPPh2)2(DMF)4][Mo6O19] (12).

Graphical abstract: [{AgL}2Mo8O26]n– complexes: a combined experimental and theoretical study

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Article information

15 Oct 2019
23 Dec 2019
First published
26 Dec 2019

Dalton Trans., 2020, Advance Article
Article type

[{AgL}2Mo8O26]n complexes: a combined experimental and theoretical study

A. V. Chupina, V. Shayapov, A. S. Novikov, V. V. Volchek, E. Benassi, P. A. Abramov and M. N. Sokolov, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT04043A

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