The effects of anion variation and ligand derivatization on silver coordination networks based upon weaker interactions.

This article presents a series of silver(I) coordination networks based upon nonchelating bidentate thioether ligands. Frameworks using AgOTs as the silver(I) starting material form two-dimensional frameworks and are quite stable as shown by differential scanning calorimetry/thermogravimetric analysis (DSC/TGA) data. The networks are sufficiently robust as to maintain the same layered motif when the basic skeleton of the ligand is sequentially derivatized with -OEt, OBu, and OHex groups. Crystal structures of the AgOTs complexes of the underivatized and bis(hexoxy) derivatives, compounds 5 and 8, respectively, are presented as well as powder X-ray diffraction (PXRD) data of the other complexes. For 5, C20H20S3O3Ag, crystal data are as follows: monoclinic, space group P2(1)/n, a = 11.8117(5) A, b = 7.8813(5) A, c = 22.3316(10) A, beta = 102.245(5) degrees, V = 2031.6(2) A(3), Z = 4. For 8, C30H44S3O6Ag, crystal data are as follows: triclinic, space group Ponebar a = 8.445(4) A, b = 10.855(5) A, c = 19.308(9) A, alpha = 84.53(1) degrees, beta = 78.76(1) degrees, gamma = 68.43(1) degrees V = 1613.9(13) A(3), Z = 2. Changing the silver(I) starting material to AgPF6 results in a shift to a one-dimensional structure, 9, as shown by X-ray crystallography and in highly compromised stability. For 9, C14H16S2N2PF6Ag, crystal data are as follows: monoclinic, space group P2/n, a = 11.9658(11) A, b = 3.9056(4) A, c = 19.6400(18) A, beta = 92.87(1) degrees, V = 916.70(15) A(3), Z = 4.

Highly selective guest uptake in a silver sulfonate network imparted by a tetragonal to triclinic shift in the solid state.

The silver sulfonate network presented herein, silver 3-pyridinesulfonate, reversibly and selectively absorbs MeCN while undergoing a major structural rearrangement. The origin of this structural flexibility is a coupling of the weak coordinating ability of the SO3 group with the geometrically pliant silver(I) center. Single crystal and powder X-ray structures of both the desolvated and solvated forms are presented in addition to the mechanism of their reversible interconversion. A heterogeneous gas chromatographic study showing selective extraction of the MeCN is also presented. Extended solid frameworks which reorder to any extent are not common but the structure presented herein transforms from a tetragonal to a triclinic crystal system. The results indicate that cooperative interactions in systems based on supposedly weaker interactions can yield softer yet functional networks with behavior unlike that observed in more rigid inorganic frameworks.