CuCu and Ag-isocyanobenzoates as novel 1D semiconducting coordination oligomers

• Published in: Dalton transactions : an international journal of inorganic chemistry 2020-09, Vol.49 (35), p.12432-1244
• Main Authors: Reguera, Leslie, Cano, Arely, Rodríguez-Hernández, Joelis, Rivera, Daniel G, Van der Eycken, Erik V, Ramírez-Rosales, Daniel, Reguera, Edilso
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d0dt02461a

Two novel semiconducting coordination oligomers with 1D chain structures, namely [H 0.07 Cu I 0.65 Cu II 0.14 (μ- p -CNC 6 H 4 CO 2 )·0.9H 2 O] n and [Ag(μ- p -CNC 6 H 4 CO 2 )] n , were obtained and characterized by XRD powder patterns, and XPS, EPR, UV-vis-NIR, IR and Raman spectroscopy. According to XRD analysis, Cu I Cu II -ICNBA is an amorphous solid, while Ag I -ICNBA crystalizes with a monoclinic unit cell in the C 2/ c space group ( Z = 4). The composition and further information of Cu I Cu II -ICNBA were obtained from the spectroscopic data. In correspondence with the quantification of terminal groups from high-resolution XPS spectra, Cu I Cu II -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 Cu I Cu II -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 μ-η 1 :η 1 - p -isocyanobenzoate ligands forming microfibers of around 120 nm (Cu I Cu II -material) and 310 nm (Ag I -material) in average diameters with optical band gaps of 2.60 eV and 2.17 eV, respectively. Novel Cu I Cu II and Ag I 1D coordination oligomers based on the μ-η 1 :η 1 - p -isocyanobenzoate ligand form microfibers with interesting semiconducting properties.