Anion-Controlled Assembly of Silver(I)/Aminobenzonitrile Compounds: Syntheses, Crystal Structures, and Photoluminescence Properties

Five coordination compounds (CCs) of the formulas {[Ag(m-abn)(2)]center dot NO3}(n) (1), {[Ag-2(m-abn)(6)]center dot(ClO4)(2)} (2), {[Ag(o-abn)(2)]center dot NO3}(n) (3), [Ag(o-abn)(2)(NO2)](n) (4), and {[Ag(o-abn)(2)]center dot PF6}(n)(5) (m-abn = 3-aminobenzonitrile, and o-abn = 2-aminobenzonitrile) were synthesized and structurally characterized by element analysis, IR, powder X-ray diffraction, and X-ray single-crystal diffraction. Structural analysis reveals that aminobenzonitrile acts as bidentate mu(2)-N,N' or monodentate mu(1)-N ligands in 1-5. Complex 1 is a ID chain comprised of C-2-symmetric [Ag(m-abn)](2) 14-membered rings. The uncoordinated NO3- anions interact with the ID chain to form a resulting 2D supramolecular sheet through N-O center dot center dot center dot N hydrogen bond. Complex 2 is a discrete binuclear Ag(I) CC incorporating concurrent bidentate mu(2)-N,N' and monodentate mu(1)-N m-abn ligands. The variation of anions from NO3- to ClO4- results in the dimensionalities of 1 and 2 decreasing from ID to OD. When using o-abn, complexes 3-5 are obtained as ID chain with C-2-symmetric [Ag(o-abn)](2) 12-membered rings, 2D sheet with coordinated mu(2)-eta(1):eta(2) NO2- anions, and 1D chain with centrosymmetric [Ag(o-abn)](2) 12-membered rings, respectively. Supramolecular interactions such as hydrogen bonding and pi center dot center dot center dot pi stacking are also proven effective in shaping the dimensionalities of the solid state structures of 1-5. Our results demonstrate that the anions are driving forces for the selection of different structures. Moreover, results about emissive behaviors and thermal stabilities of them are discussed.