Silver(I)-thioether coordination polymers constructed using asymmetric diketonate anions

The reaction of Ag-2(Fod)(2)(OH2)(H-Fod = 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione) and the thioether macrocycles [14]aneS(4) or [9]aneS(3) affords either a one-dimensional coordination polymer [Ag-2(Fod)(2)([14]aneS(4))] or a discrete mononuclear complex Ag(Fod)([9]aneS(3)), respectively. In [Ag-2(Fod)(2)([14]aneS(4))] polymeric propagation occurs through the thioether macrocycle which bridges adjacent silver(I) centres. The diketonate Fod is coordinated in both complexes, acting as an inhibitor to coordination polymer propagation, but a significant elongation of the Ag-O distance is observed for the Bu-t substituted arm of the anion. In Ag(Fod)([9]aneS(3)) this is accentuated such that the diketonate acts in a monodentate, non-chelating manner. The influence of the asymmetric nature of the diketonate anion on both local coordination environment and long-range order is discussed.