Degradation versus Expansion of the AgX Frameworks: Formation of Oligomeric and Polymeric Silver Complexes from Reactions of Bulk AgX with N,N‑Bis(diphenylphosphanylmethyl)-2-aminopyridine

Reactions of N,N-bis­(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) with [Ag­(MeCN)4]­ClO4 or AgX (X = Cl, Br, I, SCN, CN) afforded a family of oligomeric and polymeric complexes: [Ag2(MeOH)­(bdppmapy)2]­(ClO4)2 (1), [AgCl­(bdppmapy)] (2), [AgBr­(bdppmapy)] (3), [AgI­(bdppmapy)] (4), [AgSCN­(bdppmapy)] (5), [{(η2-bdppmapy)­Ag­(μ-CN)­AgCN}2(μ-bdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and [Ag2(μ-CN)­(μ-bdppmapy)2]­[Ag5(μ-CN)6] (8). Compounds 1–8 were characterized by elemental analyses, IR spectra, 1H and 31P­{1H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. Compounds 1–3 and 5 hold a one-dimensional (1D) chain in which [Ag­(MeOH)]+ or [AgX] motifs are linked by bdppmapy bridges. Compound 6 has a tetrameric framework in which two linear [(η2-bdppmapy)­Ag­(μ-CN)­AgCN] fragments are connected by a μ-bdppmapy ligand. Compound 7 contains a 1D staircase chain in which two zigzag [Ag­(μ-CN)]n chains are linked by pairs of μ-bdppmapy bridges. Compound 8 possesses an unprecedented three-dimensional (3D) structure in which the channels of one 3D anionic [Ag10(μ-CN)12]n2n– net are plugged with 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chains. The degradation versus expansion of the bulk AgX frameworks do affect the formation of [AgaXb]-based oligomers and polymers when AgX is treated with bdppmapy. The photoluminescent properties of 1–8 in the solid state were also investigated.