0000000001301062
AUTHOR
Mario Palacios-corella
Bimetallic MnIII–FeII hybrid complexes formed by a functionalized MnIII Anderson polyoxometalate coordinated to FeII: observation of a field-induced slow relaxation of magnetization in the MnIII centres and a photoinduced spin-crossover in the FeII centres
The synthesis and crystal structure of an Anderson POM functionalized with two 2,6-di(pyrazol-1-yl)-pyridine (1-bpp) ligands are reported (compound 1). High-frequency electron paramagnetic resonance (HF-EPR) and magnetic measurements show that it presents a significant negative axial zero-field splitting and field-induced slow relaxation of magnetization due to the presence of isolated MnIII anisotropic magnetic ions. Complexation of 1 with FeII gives rise to a 2D cationic network formed by Anderson POMs coordinated to two FeII ions through the two tridentate 1-bpp ligands and to other two FeII ions through two oxo ligands in compound 2, and to an anionic polymeric network formed by Anderso…
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.
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.
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…
Biodegradable Metal-Organic Framework-Based Microrobots (MOFBOTs).
Microrobots and metal–organic frameworks (MOFs) have been identified as promising carriers for drug delivery applications. While clinical applications of microrobots are limited by their low drug loading efficiencies and the poor degradability of the materials used for their fabrication, MOFs lack motility and targeted drug delivery capabilities. The combination of these two fields marks the beginning of a new era; MOF‐based small‐scale robots (MOFBOTs) for biomedical applications. Yet, biodegradability is a major hurdle in the field of micro‐ and nanoswimmers including small‐scale robots. Here, a highly integrated MOFBOT that is able to realize magnetic locomotion, drug delivery, and selec…
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.
Hexakis-adducts of [60]fullerene as molecular scaffolds of polynuclear spin-crossover molecules
A family of hexakis-substituted [60]fullerene adducts endowed with the well-known tridentate 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligand for spin-crossover (SCO) systems has been designed and synthesized. It has been experimentally and theoretically demonstrated that these molecular scaffolds are able to form polynuclear SCO complexes in solution. UV-vis and fluorescence spectroscopy studies have allowed monitoring of the formation of up to six Fe(ii)–bpp SCO complexes. In addition, DFT calculations have been performed to model the different complexation environments and simulate their electronic properties. The complexes retain SCO properties in the solid state exhibiting both thermal- and …
Influence of Proton Conducting Cations on the Structure and Properties of 2D Anilate-Based Magnets
The syntheses, structures, magnetic, and proton conductivity properties of a family of bimetallic anilate-based compounds with inserted alkylammonium cations are presented. The structures of (Me2NH2)[MnIICrIII(Br2An)3]·2H2O (1), (Et2NH2)[MnIICrIII(Br2An)3] (2), (Et3NH)[MnIICrIII(Cl2An)3] (3), and [(Et)(i-Pr)2NH]-[MnIICrIII(Br2An)3]·(CHCl3)0.5·(H2O) (4) contain a 2D anionic network formed by Mn(II) and Cr(III) ions linked through anilate ligands. In 1, 2, and 3, the hexagonal holes of this network are occupied by Me2NH2+, Et2NH2+, or Et3NH+ cations. Interestingly, the small increase of size of the templating cation in 4 ([(Et)(i-Pr)2NH]+ in the place of Me2NH2+, Et2NH2+ or Et3NH+), gives ris…
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…
CCDC 1491090: Experimental Crystal Structure Determination
Related Article: Mario Palacios-Corella, Alejandro Fernández-Espejo, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Miguel Clemente-León, Eugenio Coronado|2017|Inorg.Chem.|56|13865|doi:10.1021/acs.inorgchem.7b01965
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 1564530: Experimental Crystal Structure Determination
Related Article: Mario Palacios-Corella, Alejandro Fernández-Espejo, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Miguel Clemente-León, Eugenio Coronado|2017|Inorg.Chem.|56|13865|doi:10.1021/acs.inorgchem.7b01965
CCDC 1564529: Experimental Crystal Structure Determination
Related Article: Mario Palacios-Corella, Alejandro Fernández-Espejo, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Miguel Clemente-León, Eugenio Coronado|2017|Inorg.Chem.|56|13865|doi:10.1021/acs.inorgchem.7b01965
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
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 1856814: 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 1856808: 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 2213981: 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 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 1058520: Experimental Crystal Structure Determination
Related Article: Alexandre Abhervé, Mario Palacios-Corella, Juan Modesto Clemente-Juan, Raphael Marx, Petr Neugebauer, Joris van Slageren, Miguel Clemente-León, Eugenio Coronado|2015|J.Mater.Chem.C|3|7936|doi:10.1039/C5TC01089F
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 1058519: Experimental Crystal Structure Determination
Related Article: Alexandre Abhervé, Mario Palacios-Corella, Juan Modesto Clemente-Juan, Raphael Marx, Petr Neugebauer, Joris van Slageren, Miguel Clemente-León, Eugenio Coronado|2015|J.Mater.Chem.C|3|7936|doi:10.1039/C5TC01089F
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
Related Article: Víctor García-López, Mario Palacios-Corella, Miguel Clemente-León, Eugenio Coronado|2018|J.Coord.Chem.|71|763|doi:10.1080/00958972.2018.1430790
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 1491091: Experimental Crystal Structure Determination
Related Article: Mario Palacios-Corella, Alejandro Fernández-Espejo, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Miguel Clemente-León, Eugenio Coronado|2017|Inorg.Chem.|56|13865|doi:10.1021/acs.inorgchem.7b01965
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 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