Abstract
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.
Highlights
Cyclic trinuclear complexes with monovalent coinage metal ions have been of interest to coordination chemists for three decades [1,2,3]
The first structural characterization of pyrazolato complexes coordinated by coinage metal(I) ions was determined by Fackler and co-workers in 1988: their reported silver(I) pyrazolato complex had three intramolecular Ag···Ag distances of 3.306(2), 3.362(2), and 3.496(2) Å, forming a trinuclear complex [Ag(3,5-Ph2 pz)3 ] (3,5-Ph2 pz = 3,5-diphenyl1-pyrazolate anion) [12]
We have previously reported silver(I) pyrazolato synthesized by(XRD)
Summary
Cyclic trinuclear complexes with monovalent coinage metal ions have been of interest to coordination chemists for three decades [1,2,3]. The single-crystal characterization of the product made by the same synthetic method with aqueous NH3 was reported as [Ag(pz)]n with an Molecules 2021, 26, 1015 intramolecular Ag···Ag (argentophilic) interaction of 3.3718(7) Å , an intermolecular tion to build the hexanuclear structure can be caused by an additional stabilization of the. Subsequent ab initio complexes powder X-ray diffraction with an intramolecular Ag···Ag distance of 3.40 Å or as a dimeric trinuclear {[Ag(pz)] 3}2 and aryl-substituted pyrazoles to form trinuclear and tetranuclear structures, depending evidence indicated two possibilities: silver(I) pyrazolato complexes could exist as structure with an intermolecular Ag···Ag distance of 3.431(2) Å , depending on the on thea coordination method of synthesis and the nnature the substituents onAg the pyrazolate ring either polymer [Ag(pz)].
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