Synthesis and Structural Characterization of a Silver(I) Pyrazolato Coordination Polymer

Coinage metal(I)···metal(I) interactions are widely of interest in fields such as supramolecular assembly and unique luminescent properties, etc. Only two types of polynuclear silver(I) pyrazolato complexes have been reported, however, and no detailed spectroscopic characterizations have been reported. An unexpected synthetic method yielded a polynuclear silver(I) complex [Ag(μ-L1Clpz)]n (L1Clpz− = 4-chloride-3,5-diisopropyl-1-pyrazolate anion) by the reaction of {[Ag(μ-L1Clpz)]3}2 with (nBu4N)[Ag(CN)2]. The obtained structure was compared with the known hexanuclear silver(I) complex {[Ag(μ-L1Clpz)]3}2. The Ag···Ag distances in [Ag(μ-L1Clpz)]n are slightly shorter than twice Bondi’s van der Waals radius, indicating some Ag···Ag argentophilic interactions. Two Ag–N distances in [Ag(μ-L1Clpz)]n were found: 2.0760(13) and 2.0716(13) Å, and their N–Ag–N bond angles of 180.00(7)° and 179.83(5)° indicate that each silver(I) ion is coordinated by two pyrazolyl nitrogen atoms with an almost linear coordination. Every five pyrazoles point in the same direction to form a 1-D zig-zag structure. Some spectroscopic properties of [Ag(μ-L1Clpz)]n in the solid-state are different from those of {[Ag(μ-L1Clpz)]3}2 (especially in the absorption and emission spectra), presumably attributable to this zig-zag structure having longer but differently arranged intramolecular Ag···Ag interactions of 3.39171(17) Å. This result clearly demonstrates the different physicochemical properties in the solid-state between 1-D coordination polymer and metalacyclic trinuclear (hexanuclear) or tetranuclear silver(I) pyrazolate complexes.

Argentophilicity induced anomalous thermal expansion behavior in a 2D silver squarate

A 2D bilayer coordination polymer has been found to exhibit colossal interlayer PTE and in-plane NTE owing to argentophilic interactions.

Photochromism and photocatalysis of organic–inorganic hybrid iodoargentates modulated by argentophilic interactions

A series of organic–inorganic hybrid iodoargentates exhibit photochromic and photocatalytic properties, which could be effectively modulated by argentophilic interactions.

Advances in ligand-unsupported argentophilic interactions in crystal engineering: an emerging platform for supramolecular architectures

Ligand-unsupported argentophilic interactions are described, emphasizing reticular design and recent developments in advanced synthetic strategies, and highlighting diverse interactions that are useful for the construction of unmitigated networks.

Crystal structure of a new silver(I) coordination polymer assembled from imidazolidine-2-thione (Imt), {[Ag2(Imt)3](NO3)2}n

A new polymeric silver(I) complex of imidazolidine-2-thione (Imt), {[Ag2(Imt)3](NO3)2}n (1) was prepared and its structure was determined by single-crystal X-ray diffraction analysis. The silver atoms form infinite chains with two Ag − S(Imt) − Ag strands linked to each other by sulfur atoms of μ4-Imt ligands. Each silver(I) ion is bound to four sulfur atoms of bridging Imt ligands in a distorted tetrahedral environment. The crystal structure is stabilized by hydrogen bonding and weak argentophilic interactions. The hydrogen bonded nitrate ions connect the 1D chains to generate a 2D layer structure.