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
Jü-Hua Yang †‡, Xin-Yi Wu †, Run-Tian He †, Zhi-Gang Ren *†§ (任志刚), Hong-Xi Li †, Hui-Fang Wang †, and Jian-Ping Lang *†‡ （郎建平）
† College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of China
‡ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China
§ Institute of Materials Research and Engineering, Agency for Science, Technology and Research, 3 Research Link, Singapore 117602, Singapore
Cryst. Growth Des. 2013, 13, 2124–2134.
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.
链接：//pubs.acs.org/doi/abs/10.1021/cg4002048
