Tetramethylcyclotetraarsoxane bridging of copper(I) halide units Cu6Br6, Cu2I2, [Cu6I8](2-), and (1)(infinity)[Cu3I4-] in porous coordination polymers

The polymeric compounds (1)(infinity)[(Cu2I2(C6H5CN)(2)[cyclo-(CH3AsO)(4)]) . C6H5CN] (1) (1)(infinity)[Cu6Br6(C6H5CN)(4)(cyclo-(CH(3)ASO)(4))] (2) may be prepared by reaction of the copper(I) halide with methylcycloarsoxane ( CH3AsO)(n) in benzonitrile at 100 degrees C. 1 contains four-membered (CuI) (2) rings, 2 tricyclic Cu2Br6 units, that are connected through bridging (C H3AsO)(4) ligands into infinite chains. pi-pi Stacking of terminal C6H5CN l igands from parallel chains leads to the construction of porous frameworks, whose cavities are large enough in the case of 1 to accommodate guest C6H5 CN molecules. In the presence of CsI, the self-assembly reaction of CuI- wi th (CH3AsO)(4) in H2O-CH3OH-CH3CN (at 20 degrees C) or CH3CN (at 130 degree s C) affords [Cs(H2O)(2)][Cu3I4(cyclo-(CH3AsO)(4))(2)]. 0.5 CH3OH (3) and C s[Cu3I4(cyclo-(CH3AsO)(4))(2)] (4), whose 1- and 2-dimensional anionic coor dination polymers are linked together through respectively [Cs(cyclo-(CH3As O)(4)-kappa(4)O)(2)](+) and [Cs(Cu3I4-kappa(4)I)(cyclo-(CH3AsO)(4)-kappa(4) O)] sandwiches.