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.
Slow diffusion of AgX with O(SiMe 2 (4-Py)) 2 (L) yields unique molecular rectangles consisting of [Ag(L)] 2 X 2 (X -) NO 3 -, ClO 4 -, PF 6 -, and CF 3 SO 3 -). For the rectangular system, the transannular argentophilic (Ag-Ag) interaction competes with the interaction between Ag(I) and its anions, while the π-π interactions are constantly preserved. The strength of the argentophilic interaction is in the following order: NO 3 -> ClO 4 -> PF 6 -> CF 3 SO 3and is reversibly stretched via the anion exchange from 3.20(1) to 3.81(1) Å without the destruction of the cyclic skeleton.
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