0000000001299459
AUTHOR
Eliseo Ruiz
Enhanced bistability by guest inclusion in Fe(ii) spin crossover porous coordination polymers
Inclusion of thiourea guest molecules in the tridimensional spin crossover porous coordination polymers {[Fe(pyrazine)[M(CN)(4)]} (M = Pd, Pt) leads to novel clathrates exhibiting unprecedented large thermal hysteresis loops of ca. 60 K wide centered near room temperature.
Metal-Controlled Magnetoresistance at Room Temperature in Single-Molecule Devices
The appropriate choice of the transition metal complex and metal surface electronic structure opens the possibility to control the spin of the charge carriers through the resulting hybrid molecule/metal spinterface in a single-molecule electrical contact at room temperature. The single-molecule conductance of a Au/molecule/Ni junction can be switched by flipping the magnetization direction of the ferromagnetic electrode. The requirements of the molecule include not just the presence of unpaired electrons: the electronic configuration of the metal center has to provide occupied or empty orbitals that strongly interact with the junction metal electrodes and that are close in energy to their F…
Exchange Coupling Mediated by N–H···Cl Hydrogen Bonds: Experimental and Theoretical Study of the Frustrated Magnetic System in Bis(o-phenylenediamine)nickel(II) Chloride
The title compound crystallizes in the monoclinic P2(1)/c space group with a = 11.2470(3) A, b = 5.9034(2) A, c = 12.0886(3) A, β = 115.143(1)°, and V = 726.58(4) A(3) and consists of discrete monomeric NiCl(2)(o-phenylendiamine)(2) molecules. Each o-phen ligand coordinates in a bidentate mode with the chloride ions occupying trans positions in the resulting tetragonally distorted octahedral coordination sphere. Two discrete sets of N-H···Cl hydrogen bonds link the octahedral molecules into a two-dimensional network, with type 1 interactions linking adjacent monomers along the c axis and type 2 interactions linking monomers along the diagonals in the bc plane. Analysis of the magnetic data …
Effect of Metal Complexation on the Conductance of Single-Molecular Wires Measured at Room Temperature
The present work aims to give insight into the effect that metal coordination has on the room-temperature conductance of molecular wires. For that purpose, we have designed a family of rigid, highly conductive ligands functionalized with different terminations (acetylthiols, pyridines, and ethynyl groups), in which the conformational changes induced by metal coordination are negligible. The single-molecule conductance features of this series of molecular wires and their corresponding Cu(I) complexes have been measured in break-junction setups at room temperature. Experimental and theoretical data show that no matter the anchoring group, in all cases metal coordination leads to a shift towar…
Electronic Structure Modulation in an Exceptionally Stable Non-Heme Nitrosyl Iron(II) Spin-Crossover Complex
The highly stable nitrosyl iron(II) mononuclear complex [Fe(bztpen)(NO)](PF6)(2) (bztpen=N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethylenediamine) displays an S=1/2 S=3/2 spin crossover (SCO) behavior (T-1/2=370 K, Delta H= 12.48 kJmol(-1), Delta S=33 JK(-1) mol(-1)) stemming from strong magnetic coupling between the NO radical (S=1/2) and thermally interconverted (S=0 S=2) ferrous spin states. The crystal structure of this robust complex has been investigated in the temperature range 120-420 K affording a detailed picture of how the electronic distribution of the t(2g)-e(g) orbitals modulates the structure of the {FeNO}(7) bond, providing valuable magneto-structural and spectroscopic correlat…
Synthesis, crystal structure and magnetic properties of two oxalato-bridged dimetallic trinuclear complexes combined with a polar cation
Two isostructural heterometallic trinuclear oxalato-bridged complexes of formula C(4)[MCr(2)(ox)(6)(H(2)O)(2)]·nH(2)O (C(+) = 4-aminopyridinium; ox(2-) = oxalate dianion; M(2+) = Mn(2+), n = 3, 1; M(2+) = Co(2+), n = 3.25, 2) have been synthesized by using direct self-assembly methods combining C(3)[Cr(ox)(3)] and the chloride salts of the corresponding metal ion. The crystal structures of both compounds have been resolved by single-crystal X-ray diffraction. They crystallize in the C2/c space group [a = 11.5113(15) Å, b = 20.250(3) Å, c = 21.810(4) Å, beta = 100.447(10) degrees, V = 5161.6(3) Å(3), and Z = 4 for 1, and a = 11.4334(16) Å, b = 20.243(2) Å, c = 21.805(3) Å, beta = 101.113(9) …
Reversible Chemisorption of Sulfur Dioxide in a Spin Crossover Porous Coordination Polymer
The chemisorption of sulfur dioxide (SO2) on the Hofmann-like spin crossover porous coordination polymer (SCO-PCP) {Fe(pz)[Pt(CN)4]} has been investigated at room temperature. Thermal analysis and adsorption-desorption isotherms showed that ca. 1 mol of SO2 per mol of {Fe(pz)[Pt(CN)4]} was retained in the pores. Nevertheless, the SO2 was loosely attached to the walls of the host network and completely released in 24 h at 298 K. Single crystals of {Fe(pz)[Pt(CN)4]}·nSO2 (n ≈ 0.25) were grown in water solutions saturated with SO2, and its crystal structure was analyzed at 120 K. The SO2 molecule is coordinated to the Pt(II) ion through the sulfur atom ion, Pt-S = 2.585(4) Å. This coordination…
Borate-driven gatelike scaffolding using mesoporous materials functionalised with saccharides.
We report the development of an MCM-41 mesoporous support that is functionalised with saccharides at the pore outlets and contains the dye [Ru(bipy)(3)](2+) in the pores (solid S1; bipy = 2,2'-bipyridyl). For this hybrid system, the inhibition of mass transport of the dye from the pore voids to the bulk solution in the presence of borate is demonstrated in water at neutral pH. The formation of the corresponding boroester derivative is related to the selective reaction of borate with the appended saccharides. This control is selective and only anion borate, among several anions and cations, can act as a molecular tap and inhibit the delivery of the entrapped guest. Additionally, the S1-borat…
Spin Density Distribution in Transition Metal Complexes: Some Thoughts and Hints
Abstract The spin density distribution in transition metal complexes is discussed in qualitative terms, taking into account the coexistence of spin delocalization and spin polarization mechanisms, with the help of numerical results for several complexes obtained from density functional calculations. The covalent character of the metal-ligand bonds as well as the σ- or π-characteristics of the partially filled d orbitals must be taken into account to qualitatively predict the sign of the spin density at a particular atom within a ligand. The same patterns can be applied to binuclear complexes and can be helpful in determining the ferro- or antiferromagnetic character of the exchange coupling…
CoIILnIII dinuclear complexes (LnIII = Gd, Tb, Dy, Ho and Er) as platforms for 1,5-dicyanamide-bridged tetranuclear CoII2LnIII2 complexes: A magneto-structural and theoretical study
Five acetate-diphenoxo triply-bridged Co-II-Ln(III) complexes (Ln(I) = Gd, Tb, Dy, Ho, Er) of formula [Co(mu-L)(mu-Ac)Ln(NO3)(2)] and two diphenoxo doubly-bridged Co-II-Ln(III) complexes (Ln(III) = Gd, Tb) of formula [Co(H2O)(mu-L)Ln(NO3)(3)]center dot S (S = H2O or MeOH), were prepared in one pot reaction from the compartmental ligand N,N',N ''-trimethyl-N,N ''-bis(2-hydroxy3-methoxy-5-methylbenzyl)diethylene triamine (H2L). The diphenoxo doubly-bridged Co-II-Ln(III) complexes were used as platforms to obtain 1,5-dicyanamide-bridged tetranuclear Co-II-Ln(III) complexes (Ln(III) = Gd, Tb, Dy, Ho, Er). All exhibit ferromagnetic interactions between the Co-II and Ln(III) ions and in the case …
Exchange Coupling in Cyano-Bridged Homodinuclear Cu(II) and Ni(II) Complexes: Synthesis, Structure, Magnetism, and Density Functional Theoretical Study
The synthesis and structural characterization of several new cyano-bridged copper(II) and nickel(II) homodinuclear complexes is presented. The measure of magnetic properties for these complexes is complemented with a computational study of the exchange coupling for several model structures representing this family of compounds. The influence of several factors on the coupling constant has been examined, coordination position occupied by the bridging ligand, distortions of the coordination environment, and relative disposition of the cyanide ion with respect to the M-M vector. Comparison of experimental and calculated coupling constants allows for the rationalization of the most relevant fea…
Antiferromagnetic Interactions in Copper(II) µ-Oxalato Dinuclear Complexes: The Role of the Counterion
We report the preparation, crystal structure determination, magnetic properties and DFT calculations of five oxalato-bridged dicopper(II) complexes of formula [Cu-2(bpy)(2-)(H2O)(2)(C2O4)](CF3SO3)(2) (1), [Cu-2(bpy)(2)(C2O4)](PF6)(2) (2), [Cu-2(bpy)(2)(C2O4)](ClO4)(2) (3), [Cu-2(bpy)(2)Cl-2(C2O4)]center dot H2O (4) and [Cu-2(bpy)(2)(NO2)(2)(C2O4)] (5) (bpy = 2,2'-bipyridine and C2O42-= oxalate). Compounds 1, 2, 4 and 5 crystallize in the monoclinic system and 3 crystallizes in the triclinic system. The oxalate ligands in 1-5 adopt the bis-bidentate coordination mode and the two bpy molecules act as terminal ligands. The coordination of the counterions and the surroundings of the copper(II) …
Fatty Acid Carboxylate- and Anionic Surfactant-Controlled Delivery Systems That Use Mesoporous Silica Supports
We report the preparation of a MCM-41 mesoporous material that contains the dye [Ru(bipy) 3 ]Cl 2 (bipy= bipyridine) inside the mesopores and functionalised with suitable binding groups at the entrance of the pores. Solids S1―S3 were obtained by the reaction of the mesoporous material with N-methyl-N'-propyltrimethoxysilylimidazolium chloride, N-phenyl-N'-[3-(trimethoxysilyl)propyl]thiourea, or N-phenyl-N'-[3-(trimethoxysilyl)propy1]urea, respectively. A study of the dye delivery of these systems in buffered water (pH 7.0, 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid (HEPES), 10 ―3 mol dm ―3 ) in the presence of a family of carboxylate ions was carried out. In the interaction of …
Guest Modulation of Spin-Crossover Transition Temperature in a Porous Iron(II) Metal Organic Framework: Experimental and Periodic DFT Studies
The synthesis, structure, and magnetic properties of three clathrate derivatives of the spin-crossover porous coordination polymer {Fe(pyrazine)[Pt(CN)(4)]} (1) with five-membered aromatic molecules furan, pyrrole, and thiophene is reported. The three derivatives have a cooperative spin-crossover transition with hysteresis loops 14-29 K wide and average critical temperatures T-c=201 K (1.fur), 167 K (1.pyr), and 114.6 K (1.thio) well below that of the parent compound 1 (T-c=295 K), confirming stabilization of the HS state. The transition is complete and takes place in two steps for 1.fur, while 1.pyr and 1.thio show 50% spin transition. For 1.fur the transformation between the HS and IS (mi…
ChemInform Abstract: Spin Density Distribution in Transition Metal Complexes: Some Thoughts and Hints
Abstract The spin density distribution in transition metal complexes is discussed in qualitative terms, taking into account the coexistence of spin delocalization and spin polarization mechanisms, with the help of numerical results for several complexes obtained from density functional calculations. The covalent character of the metal-ligand bonds as well as the σ- or π-characteristics of the partially filled d orbitals must be taken into account to qualitatively predict the sign of the spin density at a particular atom within a ligand. The same patterns can be applied to binuclear complexes and can be helpful in determining the ferro- or antiferromagnetic character of the exchange coupling…
Slow Magnetic Relaxation in a Co (II)–Y (III) Single‐Ion Magnet with Positive Axial Zero‐Field Splitting
This work was supported by the MINECO (Spain) (Project CTQ2011-24478), the Junta de Andalucía (FQM-195 and Project of excellence P08-FQM-03705), and the University of Granada. E.R. and E.Cr. thank MINECO grant No. CTQ2011-23862-C02-01 and Generalitat de Catalunya grant No. 2009SGR-1459, for financial support. We would like to thank Prof. Liviu Chibotaru for providing us the SINGLE_ANISO program and Dr. Andrew Ozarowski for the EPR simulation software. E.K.B. thanks the EPSRC and Leverhulme Trust for financial support. The NHMFL is funded by the NSF, DoE, and the state of Florida. J.C. acknowledges financial support by the Spanish Ministerio de Ciencia e Innovación through projects CTQ2010-1…
Rational Design of Lanthanoid Single-Ion Magnets: Predictive Power of the Theoretical Models
We report two new single‐ion magnets (SIMs) of a family of oxydiacetate lanthanide complexes with D3 symmetry to test the predictive capabilities of complete active space ab initio methods (CASSCF and CASPT2) and the semiempirical radial effective charge (REC) model. Comparison of the theoretical predictions of the energy levels, wave functions and magnetic properties with detailed spectroscopic and magnetic characterisation is used to critically discuss the limitations of these theoretical approaches. The need for spectroscopic information for a reliable description of the properties of lanthanide SIMs is emphasised. SPINMOL ERC-CoG-647301 DECRESIM MAT2014-56143-R CTQ2014-52758-P CTQ2011-2…
Two C3-symmetric Dy3 III complexes with triple di-μ-methoxo-μ-phenoxo bridges, magnetic ground state, and single-molecule magnetic behavior
Two series of isostructural C3-symmetric Ln3 complexes Ln3·[BPh4] and Ln3·0. 33[Ln(NO3)6] (in which LnIII=Gd and Dy) have been prepared from an amino-bis(phenol) ligand. X-ray studies reveal that LnIII ions are connected by one μ2-phenoxo and two μ3-methoxo bridges, thus leading to a hexagonal bipyramidal Ln3O5 bridging core in which LnIII ions exhibit a biaugmented trigonal-prismatic geometry. Magnetic susceptibility studies and ab initio complete active space self-consistent field (CASSCF) calculations indicate that the magnetic coupling between the DyIII ions, which possess a high axial anisotropy in the ground state, is very weakly antiferromagnetic and mainly dipolar in nature. To redu…
Large Conductance Switching in a Single-Molecule Device through Room Temperature Spin-Dependent Transport
Controlling the spin of electrons in nanoscale electronic devices is one of the most promising topics aiming at developing devices with rapid and high density information storage capabilities. The interface magnetism or spinterface resulting from the interaction between a magnetic molecule and a metal surface, or vice versa, has become a key ingredient in creating nanoscale molecular devices with novel functionalities. Here, we present a single-molecule wire that displays large (>10000%) conductance switching by controlling the spin-dependent transport under ambient conditions (room temperature in a liquid cell). The molecular wire is built by trapping individual spin crossover Fe-II comple…
Metal-Organic Nanocapsules with Functionalized s-Heptazine Ligands.
A metalloorganic capsule was synthesized where the ligand is a derivative of heptazine with three carboxylic groups that are coordinated to CuII cations, forming paddle-wheel motifs. Each nanocapsule is neutral, with 12 CuII centers and 8 ligands adopting a rhombicuboctahedron shape. It has almost 3 nm diameter, and the main intermolecular interactions in the solid are π··· π stacking between the C6N7 heptazine moieties. The nanocapsules can form monolayers deposited on graphite as observed by atomic force microscopy, which confirms their stability in solution. peerReviewed
CCDC 1049852: Experimental Crystal Structure Determination
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CCDC 1049851: Experimental Crystal Structure Determination
Related Article: Miguel Julve, Alain Gleizes, Lise Marie Chamoreau, Eliseo Ruiz, Michel Verdaguer|2018|Eur.J.Inorg.Chem.||509|doi:10.1002/ejic.201700935
CCDC 684617: Experimental Crystal Structure Determination
Related Article: Daniel Aravena, Zulema Arcís Castillo, M. Carmen Muñoz, Ana B. Gaspar, Ko Yoneda, Ryo Ohtani, Akio Mishima, Susumu Kitagawa, Masaaki Ohba, José Antonio Real, Eliseo Ruiz|2014|Chem.-Eur.J.|20|12864|doi:10.1002/chem.201402292
CCDC 684616: Experimental Crystal Structure Determination
Related Article: Daniel Aravena, Zulema Arcís Castillo, M. Carmen Muñoz, Ana B. Gaspar, Ko Yoneda, Ryo Ohtani, Akio Mishima, Susumu Kitagawa, Masaaki Ohba, José Antonio Real, Eliseo Ruiz|2014|Chem.-Eur.J.|20|12864|doi:10.1002/chem.201402292
CCDC 969288: Experimental Crystal Structure Determination
Related Article: Mikko M. Hänninen, Antonio J. Mota, Daniel Aravena, Eliseo Ruiz, Reijo Sillanpää, Agustín Camón, Marco Evangelisti, Enrique Colacio|2014|Chem.-Eur.J.|20|8410|doi:10.1002/chem.201402392
CCDC 684618: Experimental Crystal Structure Determination
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CCDC 969290: Experimental Crystal Structure Determination
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CCDC 969289: Experimental Crystal Structure Determination
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CCDC 1049853: Experimental Crystal Structure Determination
Related Article: Miguel Julve, Alain Gleizes, Lise Marie Chamoreau, Eliseo Ruiz, Michel Verdaguer|2018|Eur.J.Inorg.Chem.||509|doi:10.1002/ejic.201700935
CCDC 1577872: Experimental Crystal Structure Determination
Related Article: Albert C. Aragonès, Daniel Aravena, Francisco J. Valverde-Muñoz, José Antonio Real, Fausto Sanz, Ismael Díez-Pérez, Eliseo Ruiz|2017|J.Am.Chem.Soc.|139|5768|doi:10.1021/jacs.6b11166
CCDC 684615: Experimental Crystal Structure Determination
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CCDC 1951192: Experimental Crystal Structure Determination
Related Article: Lindley Maxwell, Héctor Martínez, Alejandro Martín-Rodríguez, Silvia Gómez-Coca, Kari Rissanen, Eliseo Ruiz|2020|Inorg.Chem.|60|570|doi:10.1021/acs.inorgchem.0c03631
CCDC 684614: Experimental Crystal Structure Determination
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CCDC 1049849: Experimental Crystal Structure Determination
Related Article: Miguel Julve, Alain Gleizes, Lise Marie Chamoreau, Eliseo Ruiz, Michel Verdaguer|2018|Eur.J.Inorg.Chem.||509|doi:10.1002/ejic.201700935
CCDC 969291: Experimental Crystal Structure Determination
Related Article: Mikko M. Hänninen, Antonio J. Mota, Daniel Aravena, Eliseo Ruiz, Reijo Sillanpää, Agustín Camón, Marco Evangelisti, Enrique Colacio|2014|Chem.-Eur.J.|20|8410|doi:10.1002/chem.201402392
CCDC 987530: Experimental Crystal Structure Determination
Related Article: Daniel Aravena, Zulema Arcís Castillo, M. Carmen Muñoz, Ana B. Gaspar, Ko Yoneda, Ryo Ohtani, Akio Mishima, Susumu Kitagawa, Masaaki Ohba, José Antonio Real, Eliseo Ruiz|2014|Chem.-Eur.J.|20|12864|doi:10.1002/chem.201402292
CCDC 987531: Experimental Crystal Structure Determination
Related Article: Daniel Aravena, Zulema Arcís Castillo, M. Carmen Muñoz, Ana B. Gaspar, Ko Yoneda, Ryo Ohtani, Akio Mishima, Susumu Kitagawa, Masaaki Ohba, José Antonio Real, Eliseo Ruiz|2014|Chem.-Eur.J.|20|12864|doi:10.1002/chem.201402292
CCDC 1049850: Experimental Crystal Structure Determination
Related Article: Miguel Julve, Alain Gleizes, Lise Marie Chamoreau, Eliseo Ruiz, Michel Verdaguer|2018|Eur.J.Inorg.Chem.||509|doi:10.1002/ejic.201700935
CCDC 929061: Experimental Crystal Structure Determination
Related Article: Zulema Arcís-Castillo, Francisco J. Muñoz-Lara, M. Carmen Muñoz, Daniel Aravena, Ana B. Gaspar, Juan F. Sánchez-Royo, Eliseo Ruiz, Masaaki Ohba, Ryotaro Matsuda, Susumu Kitagawa, and José A. Real|2013|Inorg.Chem.|52|12777|doi:10.1021/ic4020477