Search

Mixed ligand dinuclear copper(II) complexes of the general formula [Cu2(Rdtc)tpmc)](ClO4)3 with octaazamacrocyclic ligand tpmc and four different heterocyclic dithiocarbamate ligands Rdtc-, as well as the complexes [Cu2(tpmc)](ClO4)4 and [Cu(tpmc)](ClO4)2 center dot 2H2O were studied in aqueous NaClO4 and HClO4 solutions by cyclic voltammetry on glassy carbon electrode. The electrochemical properties of the ligands and Cu(II) complexes were correlated with their electronic structure. Conductometric experiments showed different stoichiometry in complexation of tpmc with Cu2+ ions and transport of ions in acetonitrile and in aqueous media. These studies clarified the application of this macrocyclic ligand as ionophore in a PVC membrane copper(II) selective electrode and contributed elucidation of its sensor properties.

The simple PVC-based membrane containing N',N',N '',N '''-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane (tpmc) as an ionophore and dibutyl phthalate as a plasticizer, directly coated on a glassy carbon electrode was examined as a new sensor for Cu2+ ions. The potential response was linear within the concentration range of 1.0x10(-1)-1.0 x 10(-6)M with a Nernstian slope of 28.8 mV/decade and detection limit of 7.0 x 10(-7)M. The electrode was used in aqueous solutions over a wide pH range (1.3-6). The sensor exhibited excellent selectivity for Cu2+ ion over a number of cations and was successfully used in its determination in real samples.

Electrochemical stability of eight complexes of the general formula [co 111 Rdtc(1-8)cyclam](ClO 4 ) 2 , where cyclam=1,4,8,11-tetraazacyclotetradecane and Rdtc - (1-8)=4-morpholine (Morphdtc), 4-thiomorpholine (Timdtc), 4-piperazine (Pzdtc), N-methyl piperazine (N-Mepzdtc), piperidine (Pipdtc), 2-, 3- or 4-methylpiperidine (2-, 3- or 4-Mepipdtc) dithiocarbamates, respectively, were studied. The substances were examined in aqueous NaClO 4 solution and nonaqueous LiClO 4 in CH 3 CN solution by cyclic voltammetry. In aqueous solution, macrocyclic ligand cyclam is characterized by the anodic peak at 0.95 V. The Rdtc - ligands have two anodic peaks, one in the region 0.25-0.30 V and the other in the 0.78-0.95 V region. Absence of these anodic peaks in the case of the complexes indicates that coordination to cobalt(III) stabilizes both cyclam and Rdtc - ligands, but reversible peaks in the range -0.68 to -0.78 V support the Co(III) redox reaction. In nonaqueous solutions cyclam has one anodic peak at 1.75 V. The ligands with heteroatom in the ring (Morphdtc, Timdtc, Pzdtc, N-Mepzdtc) have two anodic peaks, while the other four ligands (Pipdtc, 2-, 3- and 4-Mepipdtc) have only one anodic peak. In nonaqueous solution again, coordination to Co(III) ion stabilizes the Rdtc - ligands and contrary to aqueous solution no Co(III) redox reaction occurs, indicating a greater stability of the complexes in this media. Finally, the electrochemical results are compared with spectroscopic data obtained previously.

1 Introduction 2 Vibrational Spectra 3 UV-vis Spectra 4 NMR Spectra 5 EPR Spectra 6 Mass Spectra 7 Molecular Characteristics and Application Perspectives 8 Acknowledgments Keywords: molecular structure of metal enolates; ligand properties, coordination activity, bond length and orientation of donor atoms - key functions in designing organic structures; enolate ions, intermediates in synthetic organic chemistry; enolic and ketonic forms of acetylacetone; vibrational spectra - IR spectra, spectral technique for detecting β-diketonate moiety and type of bonding; scandium and yttrium diketonates; nickel and palladium diketonates; UV-VIS spectra