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Redox‐active arylazothioformamide (ATF) ligands, when reacted with CuI salts, coordinate to form a variety of 1 : 1 dimers and 2 : 1 ligand‐metal complexes through a N=N−C=S chelation motif. In this study, monosubstituted (ortho/meta/para) methoxy regioisomers of ATF were synthesized and evaluated with CuI halide and BF4 salts. UV‐Vis binding association studies revealed a 2 : 1 binding association model against all species producing a para ≫ ortho > meta pattern across the methoxy substitution range. To understand why the 2 : 1 non‐linear binding model was preferred over a 1 : 1 model for CuI halide salt dimers (i. e., A2B2), a series of mechanisms were computed indicating that metal salt dimers (i. e., B+B→B2) or ligand‐metal salt‐metal salt‐ (i. e., AB+B→AB2) interactions provide favorable pathways. Combined, the data substantiate the 2 : 1 binding association mechanistically even as the substitution pattern, steric bulk, and electronics alter the coordination strength of the ligands to the CuI center.

The structure of the title complex, [Ag(C11H15N3S)2]PF6, has monoclinic (P21/c) symmetry, and the silver atom has a distorted square-planar geometry. The coordination complex crystallized from mixing silver hexafluoridophosphate with a concentrated tetrahydrofuran solution of N,N-diethylphenylazothioformamide [ATF; systematic name: 3,3-diethyl-1-(phenylimino)thiourea] under ambient conditions. The resultant coordination complex exhibits a 2:1 ligand-to-metal ratio, with the silver(I) atom having a fourfold AgN2S2 coordination sphere, with a single PF6 counter-ion. In the crystal, however, one sulfur atom from an ATF ligand of a neighboring complex coordinates to the silver atom, with a bond distance of 2.9884 (14) Å. This creates a polymeric zigzag chain propagating along the c-axis direction. The chains are linked by C—H...F hydrogen bonds, forming slabs parallel to the ac plane.

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