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

The reaction of Ag₂(Fod)₂(OH₂) (H-Fod = 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione) and the thioether macrocycles [14]aneS₄ or [9]aneS₃ affords either a one-dimensional coordination polymer [Ag₂(Fod)₂([14]aneS₄)]_∞ or a discrete mononuclear complex Ag(Fod)([9]aneS₃), respectively. In [Ag₂(Fod)₂([14]aneS₄)]_∞ 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 ^tBu substituted arm of the anion. In Ag(Fod)([9]aneS₃) 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.