Section of Inorganic and Analytical Chemistry

Ioánnina, Greece

Section of Inorganic and Analytical Chemistry

Ioánnina, Greece
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Tziouris P.A.,Section of Inorganic and Analytical Chemistry | Tsiafoulis C.G.,University of Ioannina | Vlasiou M.,University of Cyprus | Miras H.N.,University of Glasgow | And 3 more authors.
Inorganic Chemistry | Year: 2014

Reaction of hydroxylamine hydrochloride with prop-2-enamide in dichloromethane in the presence of triethylamine resulted in the isolation of the N,N′-disubstituted hydroxylamine-(diamido) ligand, 3,3′-(hydroxyazanediyl)dipropanamide (Hhydia). The ligand Hhydia was characterized by multinuclear NMR, high-resolution electrospray ionization mass spectrometry (ESI-MS), and X-ray structure analysis. Interaction of Hhydia with trans-[CrIIICl2(H2O)4]Cl·2H2O in ethanol yields the ionization isomers [CrIII(Hhydia)2]Cl3·2H2O(1·2H2O) and cis/trans-[CrIIICl2(Hhydia)2]Cl·2H2O (2·2H2O). The X-ray structure analysis of 1 revealed that the chromium atom in [CrIII(Hhydia)2]3+ is bonded to two neutral tridentate O,N,O-Hhydia ligands. The twist angle, Î, in [CrIII(Hhydia)2]3+ is 54.5(6)0, that is, very close to an ideal octahedron. The intramolecular hydrogen bonds developed between the N-OH group of the first ligand and the amidic oxygen atom of the second ligand and vice versa contribute to the overall stability of the cation [CrIII(Hhydia)2]3+. The reaction rate constant of the formation of Cr(III) complexes 1·2H2O and 2·2H2O was found to be 8.7(±0.8) × 10-5 M-1 s-1 at 25 °C in methyl alcohol and follows a first-order law kinetics based on the biologically relevant ligand Hhydia. The reaction rate constant is considerably faster in comparison with the corresponding water exchange rate constant for the hydrated chromium(III). The modification of the kinetics is of fundamental importance for the chromium(III) chemistry in biological systems. Ultraviolet-visible and electron paramagnetic resonance studies, both in solution and in the solid state, ESI-MS, and conductivity measurements support the fact that, irrespective of the solvent used in the interaction of Hhydia with trans-[CrIIICl2(H2O)4]Cl·2H2O, the ionization isomers[CrIII(Hhydia)2]Cl3·2H2O (1·2H2O) and cis/trans-[CrIIICl2(Hhydia)2]Cl·2H2O (2·2H2O) are produced.The reaction medium affects only the relevant percentage of the isomers in the solid state. The thermodynamic stability of the ionization isomers 1·2H2O and cis/trans-2·2H2O, their molecular structures as well as the vibrational spectra and the energetics of the CrIII- Hhydia/hydia- were studied by means of density functional theory calculations and found to be in excellent agreement with our experimental observations. © 2014 American Chemical Society.


Charalampou D.C.,Section of Inorganic and Analytical Chemistry | Kourkoumelis N.,Medical Physics Laboratory | Karanestora S.,Section of Organic Chemistry | Hadjiarapoglou L.P.,Section of Organic Chemistry | And 5 more authors.
Inorganic Chemistry | Year: 2014

The reaction of copper(I) halides with 2-thiouracil (TUC), 6-methyl-2-thiouacil (MTUC), and 4-methyl-2-mercaptopyrimidine (MPMTH) in the presence of triphenylphosphine (tpp) in a 1:1:2 molar ratio results in a mixed-ligand copper(I) complex with the formulas [Cu2(tpp) 4(TUC)Cl] (1), [Cu2(tpp)4(MTUC)Cl] (2), [Cu(tpp)2(MPMTH)Cl]·1/2CH3OH (3), [Cu(tpp)2(MTUC)Br] (4), and [Cu(tpp)2(MTUC)I] ·1/2CH3CN (5). The complexes have been characterized by FT-IR, 1H NMR, and UV-vis spectroscopic techniques and single-crystal X-ray crystallography. Complexes 1 and 2 are binuclear copper(I) complexes. Two phosphorus atoms from tpp ligands are coordinated to the copper(I) ions, forming two units that are linked to each other by a deprotonated TUC or MTUC chelating ligand through a sulfur bridge. A linear Cu-S-Cu moiety is formed. The tetrahedral geometry around the metal centers is completed by the nitrogen-donor atom from the TUC or MTUC ligand for the one unit, while for the other one, it is completed by the chloride anion. Two phosphorus atoms from two tpp ligands, one sulfur atom from MPMTH or MTUC ligand, and one halide anion (Cl, Br, and I) form a tetrahedron around the copper ion in 3-5 and two polymorphic forms of 4 (4a and 4b). In all of the complexes, either mono- or binuclear intramolecular O-H⋯X hydrogen bonds enhance the stability of the structures. On the other hand, in almost all cases of mononuclear complexes (with the exception of a symmetry-independent molecule in 4a), intermolecular NH⋯O hydrogen-bonding interactions lead to dimerization. Complexes 1-5 were studied for their catalytic activity for the intermolecular cycloaddition of iodonium ylides toward dihydrofuran formation by HPLC, 1H NMR, and LC-HRMS spectroscopic techniques. The results show that the geometry and halogen and ligand types have a strong effect on the catalytic properties of the complexes. The highest yield of dihydrofurans was obtained when "linear" complexes 1 and 2 were used as the catalysts. The activity of the metal complexes on the copper(I)-catalyzed and uncatalyzed intramolecular cycloaddition of iodonium ylide is rationalized through electronic structure calculation methods, and the results are compared with the experimental ones. © 2014 American Chemical Society.


Apostolopoulou A.,Technological Educational Institute of Western Greece | Apostolopoulou A.,University of Hamburg | Vlasiou M.,University of Cyprus | Tziouris P.A.,Section of Inorganic and Analytical Chemistry | And 6 more authors.
Inorganic Chemistry | Year: 2015

Corrosiveness is one of the main drawbacks of using the iodide/triiodide redox couple in dye-sensitized solar cells (DSSCs). Alternative redox couples including transition metal complexes have been investigated where surprisingly high efficiencies for the conversion of solar to electrical energy have been achieved. In this paper, we examined the development of a DSSC using an electrolyte based on square pyramidal oxidovanadium(IV/V) complexes. The oxidovanadium(IV) complex (Ph4P)2[VIVO(hybeb)] was combined with its oxidized analogue (Ph4P)[VVO(hybeb)] {where hybeb4- is the tetradentate diamidodiphenolate ligand [1-(2-hydroxybenzamido)-2-(2-pyridinecarboxamido)benzenato}and applied as a redox couple in the electrolyte of DSSCs. The complexes exhibit large electron exchange and transfer rates, which are evident from electron paramagnetic resonance spectroscopy and electrochemistry, rendering the oxidovanadium(IV/V) compounds suitable for redox mediators in DSSCs. The very large self-exchange rate constant offered an insight into the mechanism of the exchange reaction most likely mediated through an outer-sphere exchange mechanism. The [VIVO(hybeb)]2-/[VVO(hybeb)]- redox potential and the energy of highest occupied molecular orbital (HOMO) of the sensitizing dye N719 and the HOMO of [VIVO(hybeb)]2- were calculated by means of density functional theory electronic structure calculation methods. The complexes were applied as a new redox mediator in DSSCs, while the cell performance was studied in terms of the concentration of the reduced and oxidized form of the complexes. These studies were performed with the commercial Ru-based sensitizer N719 absorbed on a TiO2 semiconducting film in the DSSC. Maximum energy conversion efficiencies of 2% at simulated solar light (AM 1.5; 1000 W m-2) with an open circuit voltage of 660 mV, a short-circuit current of 5.2 mA cm-2, and a fill factor of 0.58 were recorded without the presence of any additives in the electrolyte. © 2015 American Chemical Society.

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