New iodocuprates(I) with N-heterocyclic molecules as the cations

Under the hydrothermal conditions, the reactions between CuI, KI and bp/bpp (bp=4,4′-bipiperidine, bpp=1,3-bis(4-piperidyl)propane) in an acidic alcohol solution produced three new organically templated iodocuprates(I) as [H2bp]2[Cu2I6] 1, [tmbp][Cu2I4] 2 and [tmbpp] 2 [Cu4I8]·2H2O 3 (tmbp2+=N,N,N′,N′-tetramethyl-4,4′-bipiperidinium; tmbpp2+=N,N,N′,N′-tetramethyl-1,3-bis(4-piperidyl)propane dication). X-ray analysis revealed that (i) tmbp2+ and tmbpp2+ in compounds 2 and 3 originated from the complete N-alklation of bp/bpp with CH3OH; (ii) templated by H2bp2+, the inorganic anion [Cu2I6]2− of 1 possesses a dinuclear structure, whereas templated by tmbp2+, the inorganic anion [Cu2I4]2− of 2 exhibits a one-dimensional (1D) chain structure; (iii) templated by tmbpp2+, the inorganic anion [Cu4I8]4− of 3 shows a cubane-like structure modified by four terminal I− ions. The photoluminescence analysis indicates that compounds 1 and 2 emit blue light, while compound 3 emits green light. - Graphical abstract: By employing hydrothermal in situ N-alkylation of bp/bpp with CH3OH, three new organically templated iodocuprates(I) were obtained. Display Omitted - Highlights: • Three new organically templated iodocuprates(I) were reported. • Cations tmbp2+ and tmbpp2+ originated from in situ alkylation of bp/bpp with CH3OH. • H+ and I− play a key role in alkylation of bp/bpp with CH3OH. • Photoluminescence emission for iodocuprates(I) is related to Cu···Cu interaction