BUSCADOR RECOLECTA

Digital.CSIC. Repositorio Institucional del CSIC

oai:digital.csic.es:10261/361112

The synthesis, structural characterization, topological analysis, proton conductivity, and catalytic properties are reported of two Cu(II)-based compounds, namely a dinuclear Cu(II) complex [Cu(μ-VPA)(phen)(HO)]·8HO (1) (HVPA = vinylphosphonic acid, phen = 1,10-phenanthroline) and a 1D coordination polymer [Cu(μ-SO)(phen)(HO)] (2). Their structural features and H-bonding interactions were investigated in detail, showing that the metal-organic structures of 1 and 2 are extended by multiple hydrogen bonds to more complex 2D or 1D H-bonded architectures with the kgd [Shubnikov plane net (3.6.3.6)/dual] and SP 1-periodic net (4,4)(0,2) topology, respectively. These nets are primarily driven by the H-bonding interactions involving water ligands and HO molecules of crystallization; besides, the (HO)/(HO) clusters were identified in 1. Both 1 and 2 are moderate proton conductors, with proton conductivity values, σ = 3.65 × 10 and 3.94 × 10 S·cm, respectively (measured at 80 °C and 95% relative humidity). Compounds 1 and 2 are also efficient homogeneous catalysts for the mild oxidative functionalization of C-C cycloalkanes (cyclopentane, cyclohexane, cycloheptane, and cyclooctane), namely for the oxidation by HO to give cyclic alcohols and ketones and the hydrocarboxylation by CO/HO and SO to the corresponding cycloalkanecarboxylic acids as major products. The catalytic reactions proceed under mild conditions (50-60 °C) in aqueous acetonitrile medium, resulting in up to 34% product yields based on cycloalkane substrate., Financial support was given by the European LIFE Project ADAPTAMED (LIFE14 CCA/ES/000612), (CGL2016‐80687‐R AEI/FEDER) DAMAGE, Spanish MINECO (grant JC2015‐00316 and project CGL2014‐61610‐EXP), and ERDF. The work was also partially developed as part of project ECOPOTENTIAL, which received funding from the European Union's Horizon 2020 Research and Innovation Program under grant agreement 641762.