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]
n
2n– net are plugged with 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]
n
2n+ 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.