0000000001299255
AUTHOR
Víctor García-lópez
Iron(ii) complexes of tris(2-pyridylmethyl)amine (TPMA) and neutral bidentate ligands showing thermal- and photo-induced spin crossover
Three new mononuclear Fe(ii) complexes have been prepared and characterized by the combination of tetradentate tris(2-pyridylmethyl)amine (TPMA) with three neutral bidentate ligands, such as ethylenediamine (en), 1,2-diaminopropane (pn) and 2-picolylamine (2-pic), in compounds [FeII(TPMA)(en)](ClO4)2 (1), [FeII(TPMA)(2-pic)](ClO4)2 (2) and [FeII(TPMA)(pn)](ClO4)2 (3). Structural and magnetic characterization demonstrates that the three compounds present a complete SCO behavior. The absence of strong intermolecular interactions and solvent molecules leads to reversible and gradual spin transitions. The different ligands allow tuning T1/2 from 130 K (2) to 325 K (3). The compound with the low…
Spin-crossover compounds based on iron(II) complexes of 2,6-bis(pyrazol-1-yl)pyridine (bpp) functionalized with carboxylic acid and ethyl carboxylic acid
International audience; Four new salts of the iron(II) complex of the 2,6-bis(pyrazol-1-yl)pyridine ligand functionalized with a carboxylic acid group (bppCOOH) of formulas [Fe(bppCOOH)2](BF4)2 (1(BF4)2), [Fe(bppCOOH)2](CF3SO3)2·yMe2CO (1(CF3SO3)2·yMe2CO), [Fe(bppCOOH)2](AsF6)2·yMe2CO (1(AsF6)2·yMe2CO) and [Fe(bppCOOH)2](SbF6)2·yMe2CO (1(SbF6)2·yMe2CO) have been prepared and characterized together with a more complete structural and photomagnetic characterization of the previously reported [Fe(bppCOOH)2](ClO4)2 (1(ClO4)2). Furthermore, the iron(II) complex of the ethyl ester derivative of bppCOOH (bppCOOEt) has been prepared and characterized (compound [Fe(bppCOOEt)2](ClO4)2·yMe2CO, 2(ClO4)…
Spin-crossover iron(ii) complex showing thermal hysteresis around room temperature with symmetry breaking and an unusually high T(LIESST) of 120 K.
We report a Fe(II) complex based on 4′,4′′ carboxylic acid disubstituted dipyrazolylpyridine that shows a spin-crossover close to room temperature associated to a crystallographic phase transition and the LIESST effect with a high T(LIESST) of 120 K.
Thermal- and photo-induced spin crossover in the 1D coordination polymer [Fe(4-tBupy)3][Au(CN)2]2 (4-tBupy = 4-tert-butylpyridine)
Reaction of the unidentate pyridine ligand containing a bulky t-butyl substituent with Fe2+ and [Au(CN)2]− affords a new type of spin crossover (SCO) coordination polymer in the 1D compound [Fe(4-tBupy)3][Au(CN)2]2⋅0.5H2O (1), which is formed by chains of Fe(II) complexes linked through bridging [Au(CN)2]− with three terminal 4-tBupy and one monodentate [Au(CN)2]− ligands completing the octahedral coordination around Fe(II). Longer reaction times led to the minor products [Fe(4-tBupy)2][Au(CN)2]2 (2), which presents a 2D structure more similar to that found in the other SCO compounds based on [Au(CN)2]−, and the 1D compound [Fe(4-tBupy)2(MeOH)][Au(CN)2]2 (3), in which one of the three termi…
Heteroleptic Iron(II) Spin-Crossover Complexes Based on a 2,6-Bis(pyrazol-1-yl)pyridine-type Ligand Functionalized with a Carboxylic Acid
Two new heteroleptic complexes [Fe- (1bppCOOH)(3bpp-bph)](ClO4)2·solv (1·solv, solv = various solvents; 1bppCOOH = 2,6-bis(1H-pyrazol-1-yl)- isonicotinic acid; 3bpp-bph = 2,6-bis(5-([1,1′-biphenyl]-4- yl)-1H-pyrazol-3-yl)pyridine) and [Fe(1bppCOOH)- (1bppCOOEt)](ClO4)2 ·0.5Me2CO (2·0.5Me2CO, 1bppCOOEt = ethyl 2,6-bis(1H-pyrazol-1-yl)isonicotinate) were designed and prepared. The heteroleptic compound 1· solv was obtained by the combination of stoichiometric amounts of Fe(ClO4)2, 1bppCOOH, and 3bpp-bph, and it was designed to fine-tune the spin crossover (SCO) properties with respect to the previously reported homoleptic compound [Fe(1bppCOOH)2](ClO4)2. Indeed, the introduction of a new subs…
Field-induced slow relaxation of magnetization in a mononuclear Co(II) complex of 2,6-bis(pyrazol-1-yl)pyridine functionalized with a carboxylic acid
Abstract Combining Co(II) with the 2,6-bis-(pyrazol1-yl)pyridine ligand functionalized with a carboxylic acid group (bppCOOH) results in the compound [CoII(bppCOOH)2](ClO4)2·2Me2CO, which shows a field-induced slow relaxation of magnetization as a result of the magnetic anisotropy of the distorted octahedral coordination of high-spin Co(II). Co(II)/Fe(II) solid solutions of bppCOOH have been prepared to study the influence of Co(II) on the spin crossover properties of Fe(II). Magnetic characterization of [Fe0.92Co0.08(bppCOOH)2](ClO4)2 indicates that the Cobalt dopant leads to a reduction of T1/2 and a loss of cooperativity of the spin transition.
A thermally/chemically robust and easily regenerable anilato-based ultramicroporous 3D MOF for CO 2 uptake and separation
The combination of the properly designed novel organic linker, 3,6-N-ditriazoyil-2,5-dihydroxy-1,4-benzoquinone (trz2An), with CoII ions results in a 3D ultramicroporous MOF with high CO2 uptake capacity and separation efficiency, with particular attention to CO2/N2 and CO2/CH4 gas mixtures. This material consists of 1D chains of octahedrally coordinated CoII ions linked through the anilato ligands in the equatorial positions and to the triazole substituents from two neighbouring chains in the two axial positions. This leads to a 3D microporous structure with voids with an affinity for CO2 molecules and channels that enable the selective entrance of CO2 but not of molecules with larger kine…
Redox and guest tunable spin-crossover properties in a polymeric polyoxometalate
A bifunctionalized polyoxometalate (POM), [V6O19(C16H15N6O)2]2−, which contains a redox active hexavanadate moiety covalently linked to two tridentate 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligands, has been prepared and characterized. Reaction of this hybrid molecule with Fe(II) or Zn(II) ions produces crystalline neutral 1D networks of formula Fe[V6O19(C16H15N6O)2]·solv (2) and Zn[V6O19(C16H15N6O)2]·solv (3) (solv = solvent molecules). Magnetic properties of 2 show an abrupt spin-crossover (SCO) with the temperature, which can be induced by light irradiation at 10 K (Light-Induced Excited Spin-State Trapping, LIESST effect). Interestingly, this porous and flexible structure enables reversi…
The effect of tether groups on the spin states of iron(ii)/bis[2,6-di(pyrazol-1-yl)pyridine] complexes
The synthesis of six 2,6-di(pyrazol-1-yl)pyridine derivatives bearing dithiolane or carboxylic acid tether groups is described: [2,6-di(pyrazol-1-yl)pyrid-4-yl]methyl (R)-lipoate (L1), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]ethyl (R)-lipoate (L2), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxy]ethyl (R)-lipoate (L3), N-([2,6-di(pyrazol-1-yl)pyrid-4-ylsulfanyl]-2-aminoethyl (R)-lipoamide (L4), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]acetic acid (L5) and 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]propionic acid (L6). The iron(ii) perchlorate complexes of all the new ligands exhibit gradual thermal spin-crossover (SCO) in the solid state above room temperature, except L4 who…
Insertion of single-ion magnets based on mononuclear Co(II) complexes into ferromagnetic oxalate-based networks
The 1 : 2 and 1 : 1 Co(ii) complexes of the L ligand (L = 6-(3,5-diamino-2,4,6-triazinyl)2,2'-bipyridine) with formulas [CoII(L)2](ClO4)2·0.5MeCN·Et2O (1) and [CoII(L)(CH3CN)2(H2O)](ClO4)2·MeCN (2) have been prepared. The structural and magnetic characterization of the two compounds shows that they contain octahedral high-spin Co(ii) and present a field-induced slow relaxation of the magnetization. 1 has been inserted into a bimetallic oxalate-based network leading to a novel achiral 3D compound of formula [CoII(L)2][MnIICrIII(ox)3]2·(solvate) (3) exhibiting ferromagnetic ordering below 4.6 K. EPR measurements suggest a weak magnetic coupling between the two sublattices.
Raman Spectra of ZrS2 and ZrSe2 from Bulk to Atomically Thin Layers
In the race towards two-dimensional electronic and optoelectronic devices, semiconducting transition metal dichalcogenides (TMDCs) from group VIB have been intensively studied in recent years due to the indirect to direct band-gap transition from bulk to the monolayer. However, new materials still need to be explored. For example, semiconducting TMDCs from group IVB have been predicted to have larger mobilities than their counterparts from group VIB in the monolayer limit. In this work we report the mechanical exfoliation of ZrX2 (X = S, Se) from bulk down to the monolayer and we study the dimensionality dependence of the Raman spectra in ambient conditions. We observe Raman signal from bul…
Reversible tuning of luminescence and magnetism in a structurally flexible erbium-anilato MOF.
By combining 3,6-N-ditriazolyl-2,5-dihydroxy-1,4-benzoquinone (H2trz2An) with NIR-emitting ErIII ion, two different 3D neutral polymorphic frameworks (1a and 1b), differing for the number of uncoordinated water molecules, formulated as [Er2(trz2An)3(H2O)4]n·xH2O (x = 10, a; x = 7, b), have been obtained. The structure of 1a shows layers with (6,3) topology forming six-membered rings with distorted hexagonal cavities along the bc plane. These 2D layers are interconnected through the N4 atoms of the two pendant arms of the trz2An linkers, leading to a 3D framework, where neighboring layers are eclipsed along the a axis, with hexagonal channels filled with water molecules. In 1b, layers with (…
Fe(II) spin crossover complexes of a derivative of 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) functionalized with a carboxylic acid in the 3-pyridyl position
Abstract The preparation of a new bis(pyrazol-1-yl)pyridine (1-bpp) derivative functionalized with a carboxylic acid in the 3-pyridyl position, bpp3-COOH ligand is reported together with the structure and spin-crossover (SCO) properties of [FeII(bpp3-COOH)2](ClO4)2·0.5EtOH·0.5H2O (1). Magnetic properties of 1 indicate that LS is favored. Desolvation leads to a gradual and incomplete SCO. Solvated and desolvated compounds show LIESST effect.
Iron(II) complex of 2-(1H-pyrazol-1-yl)pyridine-4-carboxylic acid (ppCOOH) suitable for surface deposition
The synthesis, structural and magnetic characterization of the tris iron(II) complex of 2-(1H-pyrazol-1-yl)pyridine-4-carboxylic acid (ppCOOH) ligand are reported in [Fe(ppCOOH)3](ClO4)2·0.5H2O·2EtOH. Single crystal structure and magnetic characterization of the bulk compound show that the low-spin state is dominant from 2 to 400 K. ESI-MS and UV–Vis spectroscopy experiments indicate that acetonitrile solutions of this complex are stable with time. ESI-MS confirms the presence of the tris complex in solution. This complex can be deposited onto SiO2 surfaces due to the presence of carboxylic acid groups by immersing the substrates into acetonitrile solutions of the complex. XPS spectra of th…
Iron(II) Complexes of 2,6-Di[4-(ethylcarboxy)pyrazol-1-yl]pyridine with Reversible Guest-Modulated Spin-Crossover Behavior
Tres solvatomorfos del complejo de hierro(II) de 2,6-di[4-(etilcarboxi)pirazol-1-il]piridina (bpCOOEt2p) de fórmulas [Fe(bpCOOEt2p)2](ClO4)2·1.5MeNO2 (1) , [Fe(bpCOOEt2p)2](ClO4)2·MeNO2 (2) y [Fe(bpCOOEt2p)2](ClO4)2·2MeNO2 (3) han sido preparados y caracterizados. Muestran interesantes propiedades de cruce de espín (SCO) que van desde transiciones de espín térmico parciales a completas y un efecto de captura de estado de espín excitado inducido por la luz (LIESST). En solvatomorph 2, se forma una estructura robusta con canales que permiten la entrada o eliminación de moléculas de solvente por difusión de vapor sin perder la cristalinidad. Por lo tanto, las muestras intercambiadas con disolv…
CCDC 2130642: Experimental Crystal Structure Determination
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CCDC 1856807: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 2059590: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Miguel Clemente-León, Eugenio Coronado|2021|J.Appl.Phys.|129|123903|doi:10.1063/5.0046998
CCDC 2059587: Experimental Crystal Structure Determination
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CCDC 2059591: Experimental Crystal Structure Determination
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CCDC 2059589: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Miguel Clemente-León, Eugenio Coronado|2021|J.Appl.Phys.|129|123903|doi:10.1063/5.0046998
CCDC 1856804: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 1917753: Experimental Crystal Structure Determination
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CCDC 1856814: Experimental Crystal Structure Determination
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CCDC 1828115: Experimental Crystal Structure Determination
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CCDC 1828114: Experimental Crystal Structure Determination
Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F
CCDC 1828117: Experimental Crystal Structure Determination
Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F
CCDC 2130640: Experimental Crystal Structure Determination
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CCDC 1828116: Experimental Crystal Structure Determination
Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F
CCDC 1856808: Experimental Crystal Structure Determination
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CCDC 2213981: Experimental Crystal Structure Determination
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CCDC 2130639: Experimental Crystal Structure Determination
Related Article: Noemi Monni, José J. Baldoví, Víctor García-López, Mariangela Oggianu, Enzo Cadoni, Francesco Quochi, Miguel Clemente-León, Maria Laura Mercuri, Eugenio Coronado|2022|Chemical Science|13|7419|doi:10.1039/D2SC00769J
CCDC 1856805: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 1944601: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Mario Palacios-Corella, Salvador Cardona-Serra, Miguel Clemente-León, Eugenio Coronado|2019|Chem.Commun.|55|12227|doi:10.1039/C9CC05988A
CCDC 1856813: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 1917752: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Mario Palacios-Corella, Verónica Gironés-Pérez, Carlos Bartual-Murgui, José Antonio Real, Eric Pellegrin, Javier Herrero-Martín, Guillem Aromí, Miguel Clemente-León, Eugenio Coronado|2019|Inorg.Chem.|58|12199|doi:10.1021/acs.inorgchem.9b01526
CCDC 1856809: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 1828113: Experimental Crystal Structure Determination
Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F
CCDC 2130641: Experimental Crystal Structure Determination
Related Article: Noemi Monni, José J. Baldoví, Víctor García-López, Mariangela Oggianu, Enzo Cadoni, Francesco Quochi, Miguel Clemente-León, Maria Laura Mercuri, Eugenio Coronado|2022|Chemical Science|13|7419|doi:10.1039/D2SC00769J
CCDC 2213982: Experimental Crystal Structure Determination
Related Article: Mario Palacios-Corella, Víctor García-López, Joao Carlos Waerenborgh, Bruno J. C. Vieira, Guillermo Mínguez Espallargas, Miguel Clemente-León, Eugenio Coronado|2023|Chemical Science|14|3048|doi:10.1039/D2SC05800F
CCDC 1584808: Experimental Crystal Structure Determination
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CCDC 1856812: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 2213983: Experimental Crystal Structure Determination
Related Article: Mario Palacios-Corella, Víctor García-López, Joao Carlos Waerenborgh, Bruno J. C. Vieira, Guillermo Mínguez Espallargas, Miguel Clemente-León, Eugenio Coronado|2023|Chemical Science|14|3048|doi:10.1039/D2SC05800F
CCDC 1856811: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 2059588: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Miguel Clemente-León, Eugenio Coronado|2021|J.Appl.Phys.|129|123903|doi:10.1063/5.0046998
CCDC 1856810: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 1917754: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Mario Palacios-Corella, Verónica Gironés-Pérez, Carlos Bartual-Murgui, José Antonio Real, Eric Pellegrin, Javier Herrero-Martín, Guillem Aromí, Miguel Clemente-León, Eugenio Coronado|2019|Inorg.Chem.|58|12199|doi:10.1021/acs.inorgchem.9b01526
CCDC 2213984: Experimental Crystal Structure Determination
Related Article: Mario Palacios-Corella, Víctor García-López, Joao Carlos Waerenborgh, Bruno J. C. Vieira, Guillermo Mínguez Espallargas, Miguel Clemente-León, Eugenio Coronado|2023|Chemical Science|14|3048|doi:10.1039/D2SC05800F
CCDC 1856806: Experimental Crystal Structure Determination
Related Article: Miguel Clemente Leon, Víctor García-López, Mario Palacios-Corella, Alexandre Abhervé, Isaac Pellicer-Carreño, Cédric Desplanches, Eugenio Coronado|2018|Dalton Trans.|47|16958|doi:10.1039/C8DT03511C
CCDC 1917750: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Mario Palacios-Corella, Verónica Gironés-Pérez, Carlos Bartual-Murgui, José Antonio Real, Eric Pellegrin, Javier Herrero-Martín, Guillem Aromí, Miguel Clemente-León, Eugenio Coronado|2019|Inorg.Chem.|58|12199|doi:10.1021/acs.inorgchem.9b01526
CCDC 1944600: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Mario Palacios-Corella, Salvador Cardona-Serra, Miguel Clemente-León, Eugenio Coronado|2019|Chem.Commun.|55|12227|doi:10.1039/C9CC05988A
CCDC 1917751: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Mario Palacios-Corella, Verónica Gironés-Pérez, Carlos Bartual-Murgui, José Antonio Real, Eric Pellegrin, Javier Herrero-Martín, Guillem Aromí, Miguel Clemente-León, Eugenio Coronado|2019|Inorg.Chem.|58|12199|doi:10.1021/acs.inorgchem.9b01526
CCDC 1944602: Experimental Crystal Structure Determination
Related Article: Víctor García-López, Mario Palacios-Corella, Salvador Cardona-Serra, Miguel Clemente-León, Eugenio Coronado|2019|Chem.Commun.|55|12227|doi:10.1039/C9CC05988A