Self-Assembly of Ag⁺/[PW₁₁NbO₄₀]^4- Complexes in Nonaqueous Solutions

Self-assembly between Ag⁺ and [PW₁₁NbO₄₀]^4- in N- and O-donor solvents (nitriles and amides) has been studied. In the case of dimethylformamide (DMF), formation of a yellow [Ag₄(DMF)₁₂][PW₁₁NbO₄₀] (1a) metastable phase and a colorless [Ag₄(DMF)₁₀][PW₁₁NbO₄₀] (1) stable phase was observed. In acetonitrile (CH₃CN), the product was [Ag(CH₃CN)₄]₂{[Ag(CH₃CN)₃]₂[PW₁₁NbO₄₀]} (2a). By contrast, [SiW₁₂O₄₀]^4- of the same size and charge as [PW₁₁NbO₄₀]^4- produces [Ag(CH₃CN)₃]₄[SiW₁₂O₄₀] (3a). Partial desolvation of 2a and 3a leads to Ag₄[PW₁₁NbO₄₀]·7.5CH₃CN (2) and Ag₄[SiW₁₂O₄₀]·7.5CH₃CN (3), respectively. The CH₃CN molecules in the structure of 2 are labile, and this compound was used as the starting material to study solvent-exchange processes in N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMA), diethylformamide (DEF), and benzonitrile (PhCN) solutions. These solvent reactions yield [Ag(DMA)₄][Ag₃(DMA)₆][PW₁₁NbO₄₀] (4), [Ag₂(NMP)₄(CH₃CN)]₂[PW₁₁NbO₄₀]·1.3NMP (5a), [Ag₂(NMP)₅]₂[PW₁₁NbO₄₀] (5b), Ag₄[PW₁₁NbO₄₀]·9.5DEF (6), and [Ag(PhCN)₄]₂[{Ag(PhCN)₃}₂PW₁₁NbO₄₀] (7). All products were isolated and characterized by single-crystal X-ray diffraction (except for 2 and 3), IR, elemental analysis, and thermogravimetric analysis techniques. The O-donor solvents favor polynuclear, solvent-bridged cationic aggregates. In the case of DMF, DMA, and DEF discrete, tri- and tetranuclear polycations are observed, while in the case of NMP, the formation of infinite polycationic structures takes place. By contrast, the N-donor solvents (CH₃CN and PhCN) favor mononuclear cations, which can exist either as distorted tetrahedral, isolated [Ag(Solv)₄]⁺ cations or as pseudotriangular {Ag(Solv)₃}⁺ units, additionally coordinated to a polyoxometalate. Screening of the luminescent properties for solid samples of 1-7 revealed that only 5a/5b and 7 are emissive. In particular, the sample containing 5a and 5b demonstrates long-lived phosphorescence with a 30 ms lifetime.