Jump to main content
Jump to site search


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

Author affiliations

Abstract

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

Back to tab navigation

Supplementary files

Article information


Submitted
15 Oct 2019
Accepted
23 Dec 2019
First published
26 Dec 2019

Dalton Trans., 2020, Advance Article
Article type
Paper

[{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

Social activity

Search articles by author

Spotlight

Advertisements