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Xavi Ribas

Publications and source records attributed to Xavi Ribas.

12 recordsLinked to original sources
PubMed2006

Redox-controlled molecular flipper based on a chiral Cu complex.

A molecular bipaddled flipper based on a tetradentate chiral Cu complex has been designed. The paddling motion of this unprecedented molecular-scale machine can be controlled by reversible oxidation of the metal center. Kinetic and computational (density functional theory) analyses provide a detailed picture of the flipper motion at the molecular scale, rationalize the switching role of the metal-ion oxidation state, and pose the basis for the fine-tuning of the dynamic motion of this new class of molecular-scale devices.

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PubMed2006

Coordination capabilities of a novel organic polychlorotriphenylmethyl monosulfonate radical.

The treatment of alpha-H-p-H-PTM (PTM = polychlorotriphenylmethane) with oleum 65% followed by deprotonation and oxidation leads to the isolation of a novel pure organic radical PTMSO3H x 3 H2O x 0.5 hexane (2). The X-ray diffraction of 2 reveals a layered structure with disordered H2O molecules between facing sulfonic acid groups. We have explored the coordination abilities of the sulfonate derivative using different metals. The treatment of 2 with mild bases yields the sulfonate radical PTMSO3Na x H2O (3). On the other hand, the new compound [Cu(py)2(H2O)4](PTMSO3)2 x 2 H2O x 2 EtOH (4) has been crystallized using Cu(II) as the metallic counterion in the presence of pyridine. The structure reveals a solvent-separated ion-pair-type compound, with no direct coordination of the metal ion with the sulfonate group, and the formation of organic layers between layers of transition metal complexes. This situation has been overcome by favoring the stabilization of the sulfonate group over the Cu(II) center by changing the pyridine ligand to cyclam. This has led to compound [Cu(cyclam)](PTMSO3)2 x 6 EtOH (5a), in which the sulfonate group acts as a monodentate axial ligand for the Cu(II) center. We have observed a single-to-single crystal rearrangement from 5a to [Cu(cyclam)](PTMSO3)2 (5b) because of the loss of the solvent of crystallization, without significant modification of the metal coordination environment. All species have been structurally and magnetically characterized, and the magnetic coupling between the organic radicals and the metal paramagnetic centers is discussed.

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PubMed2006

Copper(II) hexaaza macrocyclic binuclear complexes obtained from the reaction of their copper(I) derivates and molecular dioxygen.

Density functional theory (DFT) calculations have been carried out for a series of Cu(I) complexes bearing N-hexadentate macrocyclic dinucleating ligands and for their corresponding peroxo species (1c-8c) generated by their interaction with molecular O2. For complexes 1c-7c, it has been found that the side-on peroxodicopper(II) is the favored structure with regard to the bis(mu-oxo)dicopper(III). For those complexes, the singlet state has also been shown to be more stable than the triplet state. In the case of 8c, the most favored structure is the trans-1,2-peroxodicopper(II) because of the para substitution and the steric encumbrance produced by the methylation of the N atoms. Cu(II) complexes 4e, 5e, and 8e have been obtained by O2 oxidation of their corresponding Cu(I) complexes and structurally and magnetically characterized. X-ray single-crystal structures for those complexes have been solved, and they show three completely different types of Cu(II)2 structures: (a) For 4e, the Cu(II) centers are bridged by a phenolate group and an external hydroxide ligand. The phenolate group is generated from the evolution of 4c via intramolecular arene hydroxylation. (b) For 5e, the two Cu(II) centers are bridged by two hydroxide ligands. (c) For the 8e case, the Cu(II) centers are ligated to terminally bound hydroxide ligands, rare because of its tendency to bridge. The evolution of complexes 1c-8c toward their oxidized species has also been rationalized by DFT calculations based mainly on their structure and electrophilicity. The structural diversity of the oxidized species is also responsible for a variety of magnetic behavior: (a) strong antiferromagnetic (AF) coupling with J = -482.0 cm(-1) (g = 2.30; rho = 0.032; R = 5.6 x 10(-3)) for 4e; (b) AF coupling with J = -286.3 cm(-1) (g = 2.07; rho = 0.064; R = 2.6 x 10(-3)) for 5e; (c) an uncoupled Cu(II)2 complex for 8e.

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PubMed2005

Fine-tuning the electronic properties of highly stable organometallic Cu(III) complexes containing monoanionic macrocyclic ligands.

A family of highly stable organometallic Cu(III) complexes with monoanionic triazamacrocyclic ligands (L(i)) with general formula [CuL(i)]+ have been prepared and isolated, and their structural, spectroscopic, and redox properties thoroughly investigated. The HL(i) ligands have been designed in order to understand and quantify the electronic effects exerted by electron donor and electron-withdrawing groups on either the aromatic ring or the central secondary amine or on both. In the solid state the Cu(III) complexes were mainly characterized by single-crystal X-ray diffraction analysis, whereas in solution their structural characterization was mainly based on 1H NMR spectroscopy given the diamagnetic nature of the d(8) square-planar Cu(III) complexes. Cyclic voltammetry together with 1H NMR and UV/Vis spectroscopy have allowed us to quantify the electronic effects exerted by the ligands on the Cu(III) metal center. A theoretical analysis of this family of Cu(III) complexes has also been undertaken by DFT calculations to gain a deeper insight into the electronic structure of these complexes, which has in turn allowed a greater understanding of the nature of the UV/Vis transitions as well as the molecular orbitals involved.

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PubMed2005

Structural, magnetic, and electrical characterization of new polycrystalline phases of nickel- and platinum-doped [(DT-TTF)n][Au(mnt)2] (n = 1, 2).

Doping of spin-ladder systems by isostructural paramagnetic complexes was attempted. Despite the close isostructural nature of the pure (DT-TTF)2[M(mnt)2] (M = Au, Ni, Pt) end-members, which present a ladder structure, doping of the spin-ladder (DT-TTF)2[Au(mnt)2] with either 5% or 25% [M(mnt)2]- (M = Ni, Pt) generates two (metrically) new phases. Their markedly different crystal structures have been determined using laboratory X-ray powder diffraction data. (DT-TTF)2[Au0.75Ni0.25(mnt)2] consists of a mixed-valence compound (of triclinic symmetry), which was only detected, pure or in a mixture of phases, when [Ni(mnt)2]- was used as a dopant. Differently, the stoichiometric 1:1 [DT-TTF][Au0.75Pt0.25(mnt)2] monoclinic phase was found when [Pt(mnt)2]- (in 5% and 25%) was employed as the doping agent. Remarkably, only in the 5% Pt doping experiment, the major component of the mixture was the ladder structure compound (DT-TTF)2[Au(mnt)2] doped with minor amounts of Pt. This 5% Pt-doped specimen shows an EPR signal (g = 2.0115, DeltaHpp = 114 G at 300 K) wider than the pure compound (DT-TTF)2[Au(mnt)2], denoting exchange between the donor spins and Pt(mnt)2- centers. The electrical transport properties of the 5% Pt-doped composition at high temperatures are comparable to those of (DT-TTF)2[Au(mnt)2] with room-temperature conductivity sigma300K = 13 S/cm and thermopower S300K = 46 microV/K, with a sharp transition at 223 K similar to that previously observed in the Cu analogue at 235 K.

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PubMed2004

Correlation between crystal structure and mobility in organic field-effect transistors based on single crystals of tetrathiafulvalene derivatives.

Recently, it was reported that crystals of the organic material dithiophene-tetrathiafulvalene (DT-TTF) have a high field-effect charge carrier mobility of 1.4 cm(2)/(V x s). These crystals were formed by a simple drop-casting method, making this material interesting to investigate for possible applications in low-cost electronics. Here, organic single-crystal field-effect transistors based on materials related to DT-TTF are presented and a clear correlation between the crystal structure and the electrical characteristics is observed. The observed relationship between the mobilities in the different crystal structures is strongly corroborated by calculations of both the molecular reorganization energies and the maximum intermolecular transfer integrals. The most suitable materials described here exhibit mobilities that are among the highest reported for organic field-effect transistors and that are the highest reported for solution-processed materials.

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PubMed2004

Alkaline side-coordination strategy for the design of nickel(II) and nickel(III) bis(1,2-diselenolene) complex based materials.

The deprotonated form of the pyrazine-2,3-diselenol (pds) ligand, pds(2-), reacts with Ni(II) inorganic salts to form the nickel compounds [Ni(II)(pds)(2)](nBu(4)N)(2) (1), [Ni(II)(pds)(2)]Na(2).2H(2)O (2), and [Ni(III)(pds)(2)](2)Na(2).4H(2)O (3), depending on the reaction conditions. They are characterized by NMR, EPR, UV-vis, and IR spectroscopies, elemental analysis, cyclic voltammetry, and X-ray crystallography. The crystal structure of compound 3 shows the formation of segregated stacks of Ni(pds)(2-) units, with a strong dimerization along the stacks. The stacked fashion of the crystal packing was expected since the supramolecular forces of the alkaline side coordination to the pyrazine moieties dominate, as happens in the recently reported analogous copper system [Cu(III)(pds)(2)]Na.2H(2)O. The structure of 2 further emphasizes the alkaline coordination as the dominating supramolecular event, and an orthogonal array of 2D layers is observed. The absence of alkaline cations in complex 1 is reflected in a crystal packing with isolated complex Ni(pds)(2)(2-) units. The dimerization found in the paramagnetic Ni(III) complex 3 promotes a very strong antiferromagnetic interaction, leading to a singlet ground state.

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PubMed2004

Novel CuIII bis-1,2-dichalcogenene complexes with tunable 3D framework through alkaline cation coordination: a structural and theoretical study.

The deprotonated form of the ligands pyrazine-2,3-diselenol (pds) and pyrazine-2,3-dithiol (pdt) react with Cu(ClO(4))(2).6 H(2)O to form different Cu(III) complexes Na[Cu(III)(pds)(2)].2 H(2)O (1), Li[Cu(III)(pds)(2)].3 H(2)O (2), and Na[Cu(III)(pdt)(2)].2 H(2)O (4) depending on the countercation compound used as deprotonating agent (NaOH, LiOH). Two other Cu(III) complexes were obtained by replacement of the alkali metal cations with tetrabutylammonium (TBA(+)), namely, TBA[Cu(III)(pds)(2)] (3), and TBA[Cu(III)(pdt)(2)] (5). All complexes were characterized by (1)H and (13)C NMR and IR spectroscopy, electronic absorption, elemental analysis, cyclic voltammetry (CV), and X-ray crystallography. Electrical conductivity measurements on single crystals show that these salts exhibit insulating behavior. The crystal structure of these species revealed a lateral coordination capability of the N atoms of the pyrazine ring of both pds and pdt ligands towards the alkali metal ions, which leads to the build up of a net of coordinative bonds, hydrogen bonds, and contacts that result in the final 3D structure. Two parameters control the crystal engineering of the final 3D structures: the nature of the alkali metal countercation and the nature of the chalcogen atom (Se/S), which allow fine-tuning of complex 3D crystal lattice. Density functional calculations were performed on the [Cu(pds)(2)] and [Cu(pdt)(2)] systems to investigate the electronic structure of the complexes and understand their electronic and electrochemical behavior by studying the frontier molecular orbitals. This study also reveals whether the redox processes take place on the ligands or on the metal center, a question under continuous discussion in the literature.

Alkalies↗
PubMed2004

High mobility of dithiophene-tetrathiafulvalene single-crystal organic field effect transistors.

Single-crystal field effect transistors of the organic semiconductor dithiophene-tetrathiafulvalene (DT-TTF) were prepared by drop casting. Long, thin crystals connected two microfabricated gold electrodes, and a silicon substrate was used as a back gate. The highest hole mobility observed was 1.4 cm2/Vs, which is the highest reported for an organic semiconductor not based on pentacene. A high ON/OFF ratio of at least 7 x 105 was obtained for this device.

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