Studies of the anion effects on the molecular construction of a series of AgX complexes with bis(4-pyridyl)dimethylsilane (L) (X- = NO2-, NO3-, CF3SO3-, and PF6-) have been carried out. Formation of the skeletal bonds appears to be primarily associated with a suitable combination of bidentate N-donors of L and a variety of coordination geometries of Ag(I) ions. The L:Ag(I) ratios of the products are dependent on the nature of the polyatomic anions. The 1:1 adduct Ag(I)-L for NO2-, 3:4 adduct for NO3-, 2:3 adduct for CF3SO3-, and 1:2 adduct for PF6- have been obtained. A linear relationship between the ratio of ligand to metal and the coordinating ability of anions was observed. [Ag(NO2)(L)] has a unique sheet structure consisting of double helices, and [Ag3(L)4](NO3)3 is a 2 nm thick interwoven sheet structure consisting of nanotubes. The compound [Ag2(L)3](CF3SO3)2 affords a characteristic ladder-type channel structure, and [Ag(L)2](PF6) is a simple 2D grid structure.
Anion effects on the formation of a cross-linked Ag–Ag interaction in the molecular construction of a series of AgX complexes with bis(3-pyridyl)dimethylsilane (L) (X− = CF3SO3−, PF6−, and NO3−) have been carried out. The slow diffusion of an organic solution of L into an aqueous solution of AgX afforded [Ag(L)]X or [Ag(X)(L)]. Each L connected two Ag(I) ions (Ag–N = 2.110(5)–2.161(4) Å) to form a wave strand. For CF3SO3− and PF6− anions, each single strand cross-linked the adjacent single strands via an argentophilic interaction (Ag–Ag = 3.0551(7) Å for CF3SO3−, 3.279(1) Å for PF6−) to produce unique 2D sheets. In contrast, for the NO3− anion, the anion acts as a ligand (Ag–O3N = 2.61–2.79 Å) instead of the argentophilic interaction (Ag···Ag = 3.351(1) Å). That is, a small coordinating anion is an obstacle to form the argentophilic interaction, whereas a big noncoordinating anion favors the argentophilic interaction in the present molecular construction. For all complexes, the geometry around the Ag(I) ion is a typical T-shaped arrangement. The thermal stability can be explained in terms of the structural properties, including the argentophilic interaction.
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