Cu I Cu II and Ag I p -isocyanobenzoates as novel 1D semiconducting coordination oligomers.

Two novel semiconducting coordination oligomers with 1D chain structures, namely [(H0.07Cu0.65Cu0.14II)-Cu-I(mu-p-CNC6H4CO2)center dot 0.9H(2)O](n) and [Ag(mu-p-CNC6H4CO2)](n), were obtained and characterized by XRD powder patterns, and XPS, EPR, UV-vis-NIR, IR and Raman spectroscopy. According to XRD analysis, (CuCuII)-Cu-I-ICNBA is an amorphous solid, while Ag-I-ICNBA crystalizes with a monoclinic unit cell in the C2/c space group (Z = 4). The composition and further information of (CuCuII)-Cu-I-ICNBA were obtained from the spectroscopic data. In correspondence with the quantification of terminal groups from high-resolution XPS spectra, (CuCuII)-Cu-I-ICNBA and Ag-I-ICNBA are composed of an average of 9 and 7 monomer units, respectively, resulting in 1D-oligomers. The spectroscopic evidence indicates that (CuCuII)-Cu-I-ICNBA is better described as a non-stoichiometric coordination oligomer (where non-integer ratios of metal ions can be accommodated), while Ag-I-ICNBA is stoichiometric. In both materials, each metal center is linked by two mu-eta(1):eta(1)-p-isocyanobenzoate ligands forming microfibers of around 120 nm ((CuCuII)-Cu-I-material) and 310 nm (Ag-I-material) in average diameters with optical band gaps of 2.60 eV and 2.17 eV, respectively.