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

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Abstract

Five coordination compounds (CCs) of the formulas {[Ag(m-abn)2]·NO3}n (1), {[Ag2(m-abn)6]·(ClO4)2} (2), {[Ag(o-abn)2]·NO3}n (3), [Ag(o-abn)2(NO2)]n (4), and {[Ag(o-abn)2]·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 μ2-N,N′ or monodentate μ1-N ligands in 1–5. Complex 1 is a 1D chain comprised of C2-symmetric [Ag(m-abn)]2 14-membered rings. The uncoordinated NO3– anions interact with the 1D chain to form a resulting 2D supramolecular sheet through N–O···N hydrogen bond. Complex 2 is a discrete binuclear Ag(I) CC incorporating concurrent bidentate μ2-N,N′ and monodentate μ1-N m-abn ligands. The variation of anions from NO3– to ClO4– results in the dimensionalities of 1 and 2 decreasing from 1D to 0D. When using o-abn, complexes 3–5 are obtained as 1D chain with C2-symmetric [Ag(o-abn)]2 12-membered rings, 2D sheet with coordinated μ2-η1:η2 NO2– anions, and 1D chain with centrosymmetric [Ag(o-abn)]2 12-membered rings, respectively. Supramolecular interactions such as hydrogen bonding and π···π 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.

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