New iodometallates(I) with in situ generated organic base derivatives as countercations (M+ = Ag+, Cu+)

By employing the solvothermal in situ N-alkylation of organic bases with alcohol molecules, four new organically templated iodometallates as [L1][Ag2I4] (L12+ = 1,1,4,4-tetramethyl-1λ4,4λ4-piperazinium) 1, [L2]1.5[AgI4] (L22+ = 1,4-dibenzyl-1λ4,4λ4-diazabicyclo[2.2.2]octanium) 2, [L2]1.5[CuI4] 3 and [L3][CuI3] (L32+ = 4,4′-bis(3-methyl-1H-3λ4-imidazol-1-yl)-1,1′-biphenylium) 4 were obtained. In 1, the in situ substitution and N-alkylation of 1,4-bis(pyridin-4-ylmethyl)piperazine (L1') with CH3OH has occurred, producing L12+. Templated by L12+, Ag+ and I- aggregate into a chained iodoargentate, which can be described as a linear arrangement of AgI4 tedrahedra by sharing the edges. 2 and 3 are isostructural. In 2 and 3, the in situ N-alkylation of 1,4-diazabicyclo[2,2,2]octane (L2') with phenylmethanol has occurred, generating L22+. Templated by L22+, Ag+ (or Cu+) and I- aggregate into a mononuclear iodometallate with a tetrahedral structure. In 4, the in situ N-alkylation of 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl (L3') with CH3OH has occurred, creating L32+. Templating by L32+, Cu+ and I- aggregate into a mononuclear iodocuprate(I) with a planar trigonal structure. The photoluminescence analysis reveals that (i) at the room temperature, only 1 emits light (λem = 550 nm); (ii) at the low temperature, 4 is found to possess the photoluminescence property (λem = 546 nm at 77 K) with a ms-grade lifetime (τ = 4.915 ms).