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Abstract By employing the solvothermal in situ N -alkylation of organic bases with alcohol molecules, four new organically templated iodometallates as [L1][Ag 2 I 4 ] (L12+ = 1,1,4,4-tetramethyl-1λ4,4λ4-piperazinium) 1 , [L2] 1.5 [AgI 4 ] (L22+ = 1,4-dibenzyl-1λ4,4λ4-diazabicyclo[2.2.2]octanium) 2 , [L2] 1.5 [CuI 4 ] 3 and [L3][CuI 3 ] (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 CH 3 OH has occurred, producing L12+. Templated by L12+, Ag+ and I- aggregate into a chained iodoargentate, which can be described as a linear arrangement of AgI 4 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 CH 3 OH 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 (λ em = 550 nm); (ii) at the low temperature, 4 is found to possess the photoluminescence property (λ em = 546 nm at 77 K) with a ms-grade lifetime (τ = 4.915 ms). Graphical abstract By employing solvothermal in situ N -alkylation of organic bases with alcohol molecules, four new organically templated iodometallate(I) were obtained, and their photoluminescence properties were investigated. fx1 Highlights • Four new organically templated iodometallates(I) (M+ = Ag+, Cu+) are reported; • In situ N -alkylation of 1,4-diazabicyclo[2,2,2]octane with phenylmethanol is investigated for the first time; • In situ N -alkylation of 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl with alcohol molecules is investigated for the first time; • Their photoluminescence properties at different temperature are investigated. [ABSTRACT FROM AUTHOR]

The hydro(solvo)thermal reactions of CuI with diverse bisimidazole molecules were investigated, affording five new copper(I) iodides [Cu 4 I 4 (L1) 2 ] (L1=1,3-bis(2-methylimidazol-1-ylmethyl)benzene) 1 , [CuI(L2)] (L2=4,4′-bis(imidazolyl)biphenyl) 2 , [Cu 4 I 4 (L3)] (L3=1,3-bis(2-methylimidazol-1-yl)propane) 3 , [Cu 4 I 4 (L4) 2 ] (L4=1,4-bis(2-ethylimidazol-1-yl)butane) 4, and [Cu 4 I 4 (L5)] (L5=1,4-bis(1-imidazoly)benzene) 5 . X-ray single-crystal diffraction analysis reveals that (i) in 1 , a tetranuclear Cu-I cluster (stepped cubane) is observed, and the L1 molecule only acts as an ancillary ligand; (ii) in 2 , the L2 molecules extend the castellated Cu-I chains into a 2-D layer network with a certain thickness; (iii) in 2-D single-layer network of 3 , a 1-D Cu-I column is found, which can be viewed as a longitudinal packing of stepped Cu 4 I 4 cubanes; (vi) in 4 , the L4 molecules propagate the cubic Cu 4 I 4 cubanes into a 3-D 4-fold interpenetrated network with a cds topology; and (v) in 5 , the L5 molecules link the 1-D Cu-I ribbons into a 2-D single-layer network. The photoluminescence analysis indicates that 1 , 2 and 4 emit light (red light for 1 ; yellow light for 2 and 4 ), while 3 and 5 are not emissive. Their photoluminescence behaviors are confirmed to be related to the Cu···Cu interactions in the molecules. [ABSTRACT FROM AUTHOR]