Rational Synthesis and Characterization of Two Three‐Dimensional Metal‐Organic Frameworks Incorporating Silver Chains and 1,2,3,4,5,6‐Cyclohexanehexacarboxylate

Abstract

AbstractTwo new silver polycarboxylate coordination polymers, [Ag3(H3L)(H2O)2]n·2nH2O (1) and [Ag6L(NH3)(H2O)3]n·nH2O (2), have been obtained from the reaction of [Ag(NH3)2](OH) (freshly synthesized from Ag2O and aqueous ammonia) with cis,cis,cis,cis,cis‐1,2,3,4,5,6‐cyclohexanehexacarboxylic acid (H6L) by control of the molar ratio of starting materials. The X‐ray crystal structure analysis reveals that both of them crystallize in the triclinic space group P$\bar {1}$ with a = 6.375(4), b = 9.505(6), c = 15.097(8) Å, α = 93.249(14), β = 100.364(15), γ = 96.453(15)°, V = 891.4(9) Å3, Z = 2 for 1, and a = 8.0380(7), b = 10.1220(9), c = 13.8458(12) Å, α = 76.3450(10), β = 80.9370(10), γ = 68.7230(10)°, V = 1016.83(15) Å3, Z = 2 for 2. Complex 1 features a three‐dimensional (3D) metal‐organic framework (MOF) with one‐dimensional (1D) rectangular channels surrounded by carboxylato‐supported Ag–Ag dimers, Ag–Ag chains, and half deprotonated [H3L]3– ligands. Each [H3L]3– ligand connects eight AgI atoms. The weakly coordinated water ligands and lattice water molecules are located at the channels and form interesting 1D hydrogen‐bonded T4(2)8(2) water tapes with cyclic R86(16) (H2O)8 and R44(8) (H2O)4 units. Complex 2 is also a 3D MOF structure constructed by two types of Ag–Ag chains with Ag8 cluster units and linear Ag4 units, respectively, and fully deprotonated L6– ligands. The silver(I) atoms in 2 exhibit linear, T‐shaped, Y‐shaped, and tetrahedral coordination geometries. Each L6– ligand connects thirteen AgI atoms. The intrachain robust argentophilic interactions play a vital role in the formation of the structure. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)