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

Abstract

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.

0D to 3D Coordination Assemblies Engineered on Silver(I) Salts and 2‐(Alkylsulfanyl)azine Ligands: Crystal Structures, Dual Luminescence, and Cytotoxic Activity

“…However, the structure‐directed synthesis of the Ag (I) complexes remains now an unaddressed issue complicated by enhanced lability of Ag + ion, and some other factors. So, in the reactions of Ag (I) salts with organic ligands, the structure of a product assembled depends not only on ligand functionality, anion nature and stoichiometry, but also on the solvent effects, concentration, and crystallization conditions . These issues often lead to the lack of selectivity control over the formation of certain Ag (I) complexes or CPs .…”

Synthesis, Characterization, and Luminescent Properties of Silver(I) Complexes based on Diphosphine Ligands and 2,9‐Dimethyl‐1,10‐phenanthroline

“…The luminescent properties of d 10 metal complexes have been widely investigated as the functional materials 26,27. At ambient temperature, the solid‐state luminescent properties of complexes 1 – 5 and the corresponding original ligands were measured (Table 3, Figure 6).…”

Tetradecanuclear and Octadecanuclear Gold(I) Sulfido Clusters: Synthesis, Structures, and Luminescent Selective Tracking of Lysosomes in Living Cells

“…All reagents were commercially available and used as received. The phosphine ligand N,N -bis­(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) was prepared according to the literature procedure . The complex [Au­(tht)­Cl] (tht = tetrahydrothiophene) was synthesized according to the literature procedure .…”

“…In this work, we deliberately chose a P–N hybrid ligand, N,N -bis­(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy), because it can be used as a versatile linker in the construction of high-nuclearity Au­(I) clusters − and its pyridyl groups are anticipated to prolong the imaging period. The preformed phosphanyl-gold­(I) complex [(AuCl) 2 (bdppmapy)] ( 1 ) was treated with different amounts of Na 2 S to produce one tetradecanuclear and one octanuclear Au­(I) sulfido cluster, [Au 14 S 6 (bdppmapy) 5 ]­Cl 2 ( 2 ) and [Au 18 S 8 (bdppmapy) 6 ]­Cl 2 ( 3 ), respectively.…”