New photoluminescent iodoargentates with bisimidazole derivatives as countercations

Abstract

In this article, three bisimidazole derivatives (1,4-bis(2-ethylimidazol-1-yl)butane, L1; 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl, L2′; and 1,3-bis(2-ethylimidazol-1-yl)propane, L3) were employed to solvothermally react with AgI in an acidic environment, creating three new 1-D chained iodoargentates [H(L1)][Ag₅I₆]·DMF (DMF = N,N′-dimethylformamide) 1, [L2][Ag₃I₅] (L2²⁺ = 4,4′-di(1H-imidazol-1-ium)-1,1′-biphenyl) 2, and [H₂(L3)][Ag₂I₄] 3. L2²⁺ in 2 originated from the in situ N-alkylation of L2′ with the CH₃OH solvent. X-ray single-crystal diffraction analysis reveals that (i) in 1, Ag⁺ and I⁻ aggregate to form a 1-D tube-like iodoargentate, which exhibits the same topology as the carbon tube; (ii) the chain structure of the iodoargentate in 2 is based on a kind of trinuclear Ag–I cluster, which can be viewed as a segment of the classical cubic M₄I₄ cluster; (iii) the chain structure of the iodoargentate in 3 is simple, which can be described as a linear arrangement of the AgI₄ tetrahedra by sharing edges. The photoluminescence analysis reveals that at 77 K, (i) 1 and 2 emit strong yellow light with ms-grade photoluminescence lifetimes (5.460 ms for 1, 6.931 ms for 2); (ii) 3 possesses photochromic luminescence properties. Upon excitation at 254 nm, it emits blue-green light, whereas upon excitation at 365 nm, it emits yellow light.