Two anionic [Cu{sup I}{sub 6}X{sub 7}]{sub n}{sup n-} (X=Br and I) chain-based organic-inorganic hybrid solids with N-substituted benzotriazole ligands

Solvothermal reactions of the flexible ligand 1,6-Bi(benzotriazole)hexane with CuI and KI or CuBr and KBr in ethanol generate two hybrid compounds, namely, {l_brace}(HETA)[(Cu{sub 6}I{sub 7})(ETA){sub 2}]{r_brace}{sub n}(1) and {l_brace}K(Cu{sub 6}Br{sub 7})(BBTH){r_brace}{sub n}(2) (ETA=N-ethylbenzotriazole, HETA=protonated N-ethylbenzotriazole, BBTH=1,6-bi(benzotriazole)hexane). In 1, two [Cu{sub 3}I{sub 4}] vertex missing cubane-like subunits link each other by sharing one I atom to give a [Cu{sub 6}I{sub 7}] cluster, which further form novel 1D [Cu{sub 6}I{sub 7}]{sub n}{sup n-} anionic chain. Two in-situ generated ETA ligands finished the 4-coordinated environments of copper centers and another one discrete protonated ETA ligand keeps the charge neutrality for 1. In complex 2, bowl-shaped [Cu{sub 5}Br{sub 4}] clusters and rhomboid [Cu{sub 2}Br{sub 2}] dimers link each other to generate a [Cu{sub 6}Br{sub 7}]{sub n}{sup n-} 1D chain. BBTH ligands complete the tetrahedral spheres of Cu(I), and 7-coordinated K atoms further extend the 1D chain motifs to a 2D hybrid layer of 2. The UV-vis diffuse reflectance spectrum and luminescence measurements show that compound 1 and 2 both are potential semiconductor and photoluminescence materials. - Graphical abstract: Two unprecedented anionic [Cu{sup I}{sub 6}X{sub 7}]{sub n}{sup n-} (X=Br and I) chain-based organic-inorganic hybrid solids, namely, {l_brace}(HETA)[(Cu{sub 6}I{sub 7})(ETA){sub 2}]{r_brace}{sub n} (1) and {l_brace}K(Cu{sub 6}Br{sub 7})(BBTH){r_brace}{sub n}(2) (ETA=N-ethylbenzotriazole, HETA=protonated N-ethylbenzotriazole, BBTH=1,6-bi(benzotriazole)- hexane) have been synthesized under solvothermal reactions and characterized.