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

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