Structural tuning of tetrazole-BODIPY Ag(i) coordination compounds via co-ligand addition and counterion variation

The coordination properties of a previously described fluorescence active ligand (L), consisting of a coordinating unit (1H-tetrazol-1-yl) and a fluorophore (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivative) towards Ag(i) were investigated. Additionally, the influence of different anions (BF₄ ^-, PF₆ ^-, PF₂O₂ ^-, ClO₄ ^-, ReO₄ ^- and NO₃ ^-) and a co-ligand (CH₃CN) on the crystal structure formation and intramolecular interactions of the Ag(i) coordination compounds was studied. Beside structural investigations via single crystal X-ray diffraction, bulk characterization of the coordination compounds was conducted in both solution and solid-state, including NMR (¹H, ¹¹B, ¹⁹F, ³¹P and ¹³C), ATR-IR, UV-vis and photoluminescence spectroscopy as well as PXRD. Eleven distinct coordination compounds are reported, each falling into one of four classes: the first group (I) comprises of a mononuclear complex, whereas group (II) consists of dinuclear complexes with ligand bridged metal centers (Ag(i)) and weak intermetallic interactions (∼4 Å). Group (III) likewise includes dinuclear complexes, but the bridging mode was prevented and the Ag-Ag distance was reduced (∼3.2 Å) upon the addition of a co-ligand. Group (IV), a structurally diverse category consists of coordination polymers, which in some cases show even shorter intermetallic contacts (<3.1 Å). All investigated coordination compounds exhibit photoluminescence in the solid state, with structurally dependent emission maxima distinct from those of the ligand.