Phase diagram of calcium at high pressure and high temperature
Resistively heated diamond-anvil cells have been used together with synchrotron x-ray diffraction to investigate the phase diagram of calcium up to 50 GPa and 800 K. The phase boundaries between the Ca-I (fcc), Ca-II (bcc), and Ca-III (simple cubic, sc) phases have been determined at these pressure-temperature conditions, and the ambient temperature equation of state has been generated. The equation of state parameters at ambient temperature have been determined from the experimental compression curve of the observed phases by using third-order Birch-Murnaghan and Vinet equations. A thermal equation of state was also determined for Ca-I and Ca-II by combining the room-temperature Birch-Murn…
Precise Characterization of the Rich Structural Landscape Induced by Pressure in Multifunctional FeVO4
We have studied the high-pressure behavior of FeVO4 by means of single-crystal X-ray diffraction (XRD) and density functional theory (DFT) calculations. We have found that the structural sequence o...
Smart composite films of nanometric thickness based on copper-iodine coordination polymers. Toward sensors.
One-pot reactions between CuI and methyl or methyl 2-amino-isonicotinate give rise to the formation of two coordination polymers (CPs) based on double zig-zag Cu2I2 chains. The presence of a NH2 group in the isonicotinate ligand produces different supramolecular interactions affecting the Cu-Cu distances and symmetry of the Cu2I2 chains. These structural variations significantly modulate their physical properties. Thus, both CPs are semiconductors and also show reversible thermo/mechanoluminescence. X-ray diffraction studies carried out under different temperature and pressure conditions in combination with theoretical calculations have been used to rationalize the multi-stimuli-responsive …
Effect of linker distribution in the photocatalytic activity of multivariate mesoporous crystals
The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single-component phases or even access new functions. This approach is particularly relevant for Zr6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials are isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use high-throughput methodologi…
Crystal Structure and Magnetic Properties of 3,5-Pyridinedicarboxylate-Bridged Re(Ii)M(Ii) Heterodinuclear Complexes (M = Cu, Ni and Co)
Abstract The use of the mononuclear rhenium(II) precursor NBu4[Re(NO)Br4(H2pydc)]·i-PrOH (1) (H2pydc = 3,5-pyridinedicarboxylic acid) as a metalloligand towards Cu(II), Ni(II) and Co(II) afforded three new heterobimetallic complexes [Re(NO)Br4(μ-Hpydc)Cu(4,4′-dmbipy)2]·(CH3)2CO·0.25MeCN (2), [Re(NO)Br4(μ-Hpydc)Ni(dmphen)2]·MeCN (3) and [Re(NO)Br4(μ-Hpydc)Co(dmphen)2]·2H2O (4), respectively [4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine, dmphen = 2,9-dimethyl-1,10-phenanthroline and Bu4N+ = tetra-n-butylammonium]. The crystal structures of 1 and 2 are reported herein together with the cryomagnetic investigation of 1–4 in the temperature range of 2.0–300 K. 1 is a mononuclear compound whose str…
Synthesis, crystal structure and magnetic properties of the Re(II) complexes NBu4[Re(NO)Br4(L)] (L = pyridine and diazine type ligands).
Four novel Re(II) complexes of formula NBu4[Re(NO)Br4(L)] [NBu4(+) = tetra-n-butylammonium cation and L = pyridine (1), pyrazine (2), pyrimidine (3), pyridazine (4)] have been prepared by a substitution reaction involving NBu4[Re(NO)Br4(EtOH)] and L. Their crystal structures have been determined by single crystal X-ray diffraction. They are all mononuclear complexes whose structure is made up of [Re(NO)Br4L](-) anions and NBu4(+) cations. Each Re(II) ion is six-coordinate with four bromide ligands, a linear nitrosyl group and one monodentate nitrogen donor L building a tetragonally distorted octahedral surrounding. The Re-Br bond distances cover a narrow range [2.5048(8)-2.5333(5) Å] and th…
Comment on “High-pressure x-ray diffraction study of YBO3/Eu3+, GdBO3, and EuBO3: Pressure-induced amorphization in GdBO3” [J. Appl. Phys. 115, 043507 (2014)]
High-pressure x-ray diffraction studies on vaterite-type borates were reported on the above paper and their room-temperature P-V equation of state (EOS) determined. YBO3/Eu3+ and GdBO3 were found to have bulk moduli around 320 GPa, 90% larger than the bulk modulus obtained for EuBO3. Consequently, it was stated that vaterite-type borates are as incompressible as cubic BN. Such a different compressional behavior of isomorphic borates contradicts the known systematic of related borates. Here, we show that the conclusions reported on the above article could be hindered by experimental errors and artifacts. Ab initio calculations support our criticism giving similar bulk moduli (130–141 GPa) in…
Crystal structure and magnetic properties of the single-μ-chloro copper(II) chain [Cu(bipy)Cl2] (bipy = 2,2′-bipyridine)
Abstract The crystal and molecular structure of the copper(II) chain [Cu(bipy)Cl2] (1) (bipy = 2,2′-bipyridine) has been determined by X-ray diffraction methods. The crystal structure of 1 consists of neutral single chloro-bridged copper(II) chains with alternating short and long Cu–Cl distances through a screw axis parallel to a. The copper surrounding is best described as distorted square pyramidal, the equatorial plane being built by the two nitrogen atoms of the chelating bipy and two chlorine atoms (one terminal and the other bridging), whereas the apical position is filled by the bridging chlorine atom from the symmetry-related adjacent unit. The equatorial Cu–Cl bonds (2.291(3) and 2…
Permanent Porosity in Hydroxamate Titanium-Organic Polyhedra.
Following the synthesis of hydroxamate titanium–organic frameworks, we now extend these siderophore-type linkers to the assembly of the first titanium–organic polyhedra displaying permanent porosity. Mixed-linker versions of this molecular cage (cMUV-11) are also used to demonstrate the effect of pore chemistry in accessing high surface areas of near 1200 m2·g–1.
Peptide metal-organic frameworks under pressure: flexible linkers for cooperative compression
We investigate the structural response of a dense peptide metal-organic framework using in situ powder and single-crystal X-ray diffraction under high-pressures. Crystals of Zn(GlyTyr)2 show a reversible compression by 13% in volume at 4 GPa that is facilitated by the ability of the peptidic linker to act as a flexible string for a cooperative response of the structure to strain. This structural transformation is controlled by changes to the conformation of the peptide, which enables a bond rearrangement in the coordination sphere of the metal and changes to the strength and directionality of the supramolecular interactions specific to the side chain groups in the dipeptide sequence. Compar…
The crystal structure and magnetic properties of 3-pyridinecarboxylate-bridged Re(ii)M(ii) complexes (M = Cu, Ni, Co and Mn)
The novel Re(II) complex NBu4[Re(NO)Br4(Hnic)] (1) and the heterodinuclear compounds [Re(NO)Br4(μ-nic)Ni(dmphen)2]·½CH3CN (2), [Re(NO)Br4(μ-nic)Co(dmphen)2]·½MeOH (3), [Re(NO)Br4(μ-nic)Mn(dmphen)(H2O)2]·dmphen (4), [Re(NO)Br4(μ-nic)Cu(bipy)2] (5) [Re(NO)Br4(μ-nic)Cu(dmphen)2] (5') (NBu4(+) = tetra-n-butylammonium cation, Hnic = 3-pyridinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline, bipy = 2,2'-bipyridine) have been prepared and the structures of 1-5 determined using single crystal X-ray diffraction. The structure of 1 consists of [Re(NO)Br4(Hnic)](-) anions and NBu4(+) cations. Each Re(II) is six-coordinate with four bromide ligands, a linear nitrosyl group and a nitrogen ato…
Chemical Engineering of Photoactivity in Heterometallic Titanium–Organic Frameworks by Metal Doping
[EN] We report a new family of titanium-organic frameworks that enlarges the limited number of crystalline, porous materials available for this metal. They are chemically robust and can be prepared as single crystals at multi-gram scale from multiple precursors. Their heterometallic structure enables engineering of their photoactivity by metal doping rather than by linker functionalization. Compared to other methodologies based on the post-synthetic metallation of MOFs, our approach is well-fitted for controlling the positioning of dopants at an atomic level to gain more precise control over the band-gap and electronic properties of the porous solid. Changes in the band-gap are also rationa…
Bio-inspired Ni dinuclear complexes as heterogeneous catalysts for hydrogen evolution
Abstract A major challenge in the sustainable production of hydrogen is lowering the electrochemical overpotential and the activation energy of the hydrogen evolution reaction. Some enzymes have two metallic Ni centers and catalyze this reaction with high activity. Taking inspiration from them, we have developed two novel dinuclear Ni(II) complexes, Ni-PATIO and Ni-PACO, with promise as molecular catalysts. Ni-PACO exhibits a square-planar geometry for both Ni(II) and two-fold rotational symmetry both in solid and solution states, whereas Ni-PATIO displays one square-planar Ni(II) center and one octahedral Ni(II) configuration, which confer it magnetic properties. We show that both complexe…
self-consistent approach to describe unit-cell-parameter and volume variations with pressure and temperature
A method is presented for the self-consistent description of the variations of unit-cell parameters of crystals with pressure and temperature.
A new eight-coordinate complex of manganese(II): synthesis, crystal structure, spectroscopy and magnetic properties of [Mn(Hoxam)2(H2O)4] (H2oxam=oxamic acid)
Abstract The crystal structure of an eight-coordinate manganese(II) compound containing oxamato and water molecules as ligands [Mn(Hoxam)2(H2O)4], were H2oxam=oxamic acid, has been determined by X-ray diffraction on single-crystals. The coordinated oxygen atoms are located at the vertices (corners) of a distorted bicapped trigonal antiprism. Hydrogen bonding is responsible for an extended 3D-network. The magnetic susceptibility data of the compound have been investigated. χMT follows the Curie law, at very low temperatures χMT decreases smoothly due to weak intermolecular interactions and/or due to a small zero field splitting of the sextuplet spin state of the Mn(II).
Phase Behavior of TmVO4 under Hydrostatic Compression: An Experimental and Theoretical Study
We present a structural and optical characterization of magnetoelastic zircon-type TmVO4 at ambient pressure and under high pressure. The properties under high pressure have been determined experimentally under hydrostatic conditions and theoretically using density functional theory. By powder X-ray diffraction we show that TmVO4 undergoes a first-order irreversible phase transition to a scheelite structure above 6 GPa. We have also determined (from powder and single-crystal X-ray diffraction) the bulk moduli of both phases and found that their compressibilities are anisotropic. The band gap of TmVO4 is found to be Eg = 3.7(2) eV. Under compression the band gap opens linearly, until it unde…
High-Pressure Single-Crystal X-ray Diffraction of Lead Chromate: Structural Determination and Reinterpretation of Electronic and Vibrational Properties.
We have investigated the high-pressure behavior of PbCrO4. In particular, we have probed the existence of structural transitions under high pressure (at 4.5 GPa) by single-crystal X-ray diffraction and density functional theory calculations. The structural sequence of PbCrO4 is different than previously determined. Specifically, we have established that PbCrO4, under pressure, displays a monoclinic-tetragonal phase transition, with no intermediate phases between the low-pressure monoclinic monazite structure (space group P21/ n) and the high-pressure tetragonal structure. The crystal structure of the high-pressure polymorph is, for the first time, undoubtedly determined to a tetragonal sche…
CCDC 1826854: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1588161: Experimental Crystal Structure Determination
Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D
CCDC 1826851: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 2089144: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Javier González-Platas, Miguel Julve, Francesc Lloret, Carlos Kremer, Alicia Cuevas|2021|Polyhedron|208|115414|doi:10.1016/j.poly.2021.115414
CCDC 2065593: Experimental Crystal Structure Determination
Related Article: Alejandro Cabrera-García, Vincent Blay, Rubén Blay-Roger, Ángel G. Ravelo, Javier González-Platas, M. Carmen Arévalo, Joaquín Sanchiz, Pedro Martín-Zarza|2021|Chem.Eng.Journal|420|130342|doi:10.1016/j.cej.2021.130342
CCDC 1055519: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Francesc Lloret, Miguel Julve, Carlos Kremer|2015|Dalton Trans.|44|11636|doi:10.1039/C5DT01321F
CCDC 1055523: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Francesc Lloret, Miguel Julve, Carlos Kremer|2015|Dalton Trans.|44|11636|doi:10.1039/C5DT01321F
CCDC 1055520: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Francesc Lloret, Miguel Julve, Carlos Kremer|2015|Dalton Trans.|44|11636|doi:10.1039/C5DT01321F
CCDC 1826848: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1588164: Experimental Crystal Structure Determination
Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D
CCDC 1826858: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1826857: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1826853: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1588162: Experimental Crystal Structure Determination
Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D
CCDC 1588165: Experimental Crystal Structure Determination
Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D
CCDC 1055521: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Francesc Lloret, Miguel Julve, Carlos Kremer|2015|Dalton Trans.|44|11636|doi:10.1039/C5DT01321F
CCDC 1826849: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 2023345: Experimental Crystal Structure Determination
Related Article: Belén Lerma-Berlanga, Carolina R. Ganivet, Neyvis Almora-Barrios, Sergio Tatay, Yong Peng, Josep Albero, Oscar Fabelo, Javier González-Platas, Hermenegildo García, Natalia M. Padial, Carlos Martí-Gastaldo|2021|J.Am.Chem.Soc.|143|1798|doi:10.1021/jacs.0c09015
CCDC 2089145: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Javier González-Platas, Miguel Julve, Francesc Lloret, Carlos Kremer, Alicia Cuevas|2021|Polyhedron|208|115414|doi:10.1016/j.poly.2021.115414
CCDC 1826850: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 925074: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Ricardo Faccio, Francesc Lloret, Miguel Julve, Carlos Kremer|2013|Dalton Trans.|42|15361|doi:10.1039/C3DT51699G
CCDC 1826847: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1826855: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1826852: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 925073: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Ricardo Faccio, Francesc Lloret, Miguel Julve, Carlos Kremer|2013|Dalton Trans.|42|15361|doi:10.1039/C3DT51699G
CCDC 1588166: Experimental Crystal Structure Determination
Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D
CCDC 1826846: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1055522: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Francesc Lloret, Miguel Julve, Carlos Kremer|2015|Dalton Trans.|44|11636|doi:10.1039/C5DT01321F
CCDC 1826856: Experimental Crystal Structure Determination
Related Article: Javier Conesa-Egea, Noemí Nogal, José Ignacio Martínez, Vanesa Fernández-Moreira, Ulises R. Rodríguez-Mendoza, Javier González-Platas, Carlos J. Gómez-García, Salomé Delgado, Félix Zamora, Pilar Amo-Ochoa|2018|Chemical Science|9|8000|doi:10.1039/C8SC03085E
CCDC 1588163: Experimental Crystal Structure Determination
Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D
CCDC 1588160: Experimental Crystal Structure Determination
Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D
CCDC 925071: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Ricardo Faccio, Francesc Lloret, Miguel Julve, Carlos Kremer|2013|Dalton Trans.|42|15361|doi:10.1039/C3DT51699G
CCDC 925072: Experimental Crystal Structure Determination
Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Ricardo Faccio, Francesc Lloret, Miguel Julve, Carlos Kremer|2013|Dalton Trans.|42|15361|doi:10.1039/C3DT51699G