Crystal engineering in confined spaces. A novel method to grow crystalline metal phosphonates in alginate gel systems

In this paper we report a crystal growth method for metal phosphonate frameworks in alginate gels. It consists of a metalcontaining alginate gel, in which a solution of phosphonate ligand is slowly diffused. Crystals of metal phosphonate products are formed inside the gel. We have applied this for a variety of metal ions (alkaline-earth metals, transition metals and lanthanides) and a number of polyphosphonic acid and mixed carboxy/phosphonic acid ligands.Proyecto nacional MAT2010-1517

Imidazole-containing Co2+ and Ni2+ etidronates: crystal structures and electrochemical behaviour

Proyecto Nacional PID2019-110249RB-I00, PAIDI2020 de la Junta de Andalucia, Ayudas del Plan Propio de Investigación de la Universidad de Málaga para la contratación predoctoral (PRE2020-094459).Metal phosphonates-based coordination polymers (CPs) are known to exhibit versatile structural diversity and functionality. Thus, they have been used, among other applications, as electrocatalyst precursors for both, PEMFCs and electrolysers. In this work, we report the synthesis, crystal structure and electrochemical properties of imidazole-containing Co2+, Ni2+ and Zn2+ derivatives of the etidronic acid, (HO)2P(O)-C(CH3)(OH)-P(O)(OH)2 (ETID). Analyses of the crystal structures reveals that these solids are 1D, in which the imidazole molecules form part of the coordination sphere of the cations (Co2+, Ni2+) or act as charge-compensating imidazolium cations (Zn2+). Co2+ and Ni2+ solids were pyrolysed under 5% H2/Ar atmosphere at different temperatures. The resulting metal phosphides were tested as electrocatalysts for the Oxygen Evolution and Reduction Reactions (OER and ORR, respectively) and the Hydrogen Evolution Reaction (HER). Preliminary results indicate that Co2+ derivatives exhibit better performance.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Common Structural Features in Calcium Hydroxyphosphonoacetates. A High-Throughput Screening

R,S-Hydroxyphosphonoacetic acid (H3HPA) is an inexpensive multidentate organic ligand widely used for the preparation of organo-inorganic hybrid materials. There are reports of several crystal structures and the variability of the resulting frameworks is strikingly high, in contrast with the simplicity of the ligand. In an attempt to investigate and rationalize some salient structural features of the crystal structures, we have carried out a systematic high-throughput study of the reaction of H3HPA with Ca2þ in aqueous solutions (pH values ranging 1.0-7.5) at room temperature and hydrothermally at 180 ºC. The tested synthetic conditions yielded five crystalline singlephase Ca-H3HPA hybrids: Ca3(O3PCHOHCOO)2 · 14H2O (1), Ca(HO3PCHOHCOO) · 3H2O (2), Ca5(O3PCHOHCOO)2(HO3PCHOHCOO)2 · 6H2O (3), CaLi(O3PCHOHCOO) (4), and Ca2Na(O3PCHOHCOO (HO3PCHOHCOO) ·1.5H2O(5). Four new crystal structures, 2-5, are reported (three frompowder diffraction data and one from single-crystal data), which allowed us to unravel some key common structural features. The Ca-H3HPA hybrids without an extra alkaline cation, 1-3, contain a common structural motif, which has been identified as a linear Ca-H3HPA-Ca-H3HPA-Ca trimer. This inorganic motif has a central Ca2+ in a distorted octahedral environment, whereas the two side Ca2+ cations are in an eight-coordinated oxygen-rich environment. The H3HPA ligands are chelating the central Ca2+ through two pairs of carboxylate and phosphonate oxygen atoms forming six-membered rings, Ca-O-C-C-P-O-Ca. This coordination mode allows the peripheral Ca(II) ions to bind the ligand through the -OH group and the other carboxylate oxygen, forming a fivemembered ring, Ca-O-C-C-O-Ca. The presence of alkaline cations, Li+ and Na+, disrupt this common structural feature leading to highly dense frameworks. Finally, similarities (and differences) between Ca-H3HPA and Cd-H3HPA hybrids are also discussed.Proyectos nacionales MAT2009-07016 y MAT2010-15175 (MICINN, España

Tuning Proton Conductivity in Alkali Metal Phosphonocarboxylates by Cation Size-Induced and Water-Facilitated Proton Transfer Pathways

The structural and functional chemistry of a family of alkali-metal ions with racemic R,S-hydroxyphosphonoacetate (M-HPAA; M = Li, Na, K, Cs) are reported. Crystal structures were determined by X-ray data (Li+, powder diffraction following an ab initio methodology; Na+, K+, Cs+, single crystal). A gradual increase in dimensionality directly proportional to the alkali ionic radius was observed. [Li3(OOCCH(OH)PO3)-(H2O)4]·H2O (Li-HPAA) shows a 1D framework built up by Li-ligand “slabs” with Li+ in three different coordination environments (4-, 5-, and 6-coordinated). Na-HPAA, Na2(OOCCH(OH)PO3H)(H2O)4, exhibits a pillared layered “house of cards” structure, while K-HPAA, K2(OOCCH(OH)PO3H)(H2O)2, and Cs-HPAA, Cs(HOOCCH(OH)-PO3H), typically present intricate 3D frameworks. Strong hydrogen-bonded networks are created even if no water is present, as is the case in Cs-HPAA. As a result, all compounds show proton conductivity in the range 3.5 × 10−5 S cm−1 (Cs-HPAA) to 5.6 × 10−3 S cm−1 (Na-HPAA) at 98% RH and T = 24 °C. Differences in proton conduction mechanisms, Grothuss (Na+ and Cs+) or vehicular (Li+ and K+), are attributed to the different roles played by water molecules and/or proton transfer pathways between phosphonate and carboxylate groups of the ligand HPAA. Upon slow crystallization, partial enrichment in the S enantiomer of the ligand is observed for Na-HPAA, while the Cs-HPAA is a chiral compound containing only the S enantiomer.Proyectos nacionales MAT2010-15175 y MAT2013-41836-

Synthesis and structural characterization of 2-D layered copper(II) styrylphosphonate coordination polymers

We report the synthesis, physicochemical characterization, and crystal structure of Cu-SP (SP = styrylphosphonic acid, H2O3PCH=CH2(C6H5)), the first reported example of a metal derivative of SP. The starting SP acid was fully characterized by X-ray single-crystal diffractometry, elemental analysis (C and H), 31P-NMR, 13C-NMR, 1H-NMR, HPLC, UV–vis, MS, TG, and FT-IR spectroscopy. The copper(II) derivative was synthesized and characterized by DTA-TG and FT-IR, and also its structure was determined from powder data. The crystal structure was refined by the Rietveld method. The crystal structure of Cu-SP shows a layered 2-D architecture, where the organic moieties are pointed toward the interlamellar space. The inorganic layers are composed of Cu2+ dimers, where the coordination geometry of Cu2+ can be described as distorted trigonal bipyramid. The three coplanar oxygens (O2, O3, and O3) have bond distances of 2.165(9), 1.982(9), and 2.103(11) Å, respectively. The bond lengths for the apical oxygens (O1 and O2) are 1.908(13) and 1.996(11) Å, respectively.Proyecto nacional MAT2010-1517

Phase Transformation Dynamics in Sulfate-Loaded Lanthanide Triphosphonates. Proton Conductivity and Application as Fillers in PEMFCs

Phase transformation dynamics and proton conduction properties are reported for cationic layer-featured coordination polymers derived from the combination of lanthanide ions (Ln3+) with nitrilo-tris(methylenephosphonic acid) (H6NMP) in the presence of sulfate ions. Two families of materials are isolated and structurally characterized, i.e., [Ln2(H4NMP)2(H2O)4](HSO4)2·nH2O (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb; n = 4−5, Series I) and [Ln(H5NMP)]SO4· 2H2O (Ln = Pr, Nd, Eu, Gd, Tb; Series II). Eu/Tb bimetallic solid solutions are also prepared for photoluminescence studies. Members of families I and II display high proton conductivity (10−3 and 10−2 S·cm−1 at 80 °C and 95% relative humidity) and are studied as fillers for Nafion-based composite membranes in PEMFCs, under operating conditions. Composite membranes exhibit higher power and current densities than the pristine Nafion membrane working in the range of 70−90 °C and 100% relative humidity and with similar proton conductivity.Proyectos de Ministero de Ciencia e Innovación MAT2016-77648-R (MICINN/FEDER); PID2019-110249RB-I00 (MICINN/FEDER) y la Junta de Andalucía (FQM113). Funding for open access change: Universidad de Málaga/ CBU

Monte Carlo simulations of an impurity band model for III-V diluted magnetic semiconductors

We report the results of a Monte Carlo study of a model of (III,Mn)V diluted magnetic semiconductors which uses an impurity band description of carriers coupled to localized Mn spins and is applicable for carrier densities below and around the metal-insulator transition. In agreement with mean field studies, we find a transition to a ferromagnetic phase at low temperatures. We compare our results for the magnetic properties with the mean field approximation, as well as with experiments, and find favorable qualitative agreement with the latter. The local Mn magnetization below the Curie temperature is found to be spatially inhomogeneous, and strongly correlated with the local carrier charge density at the Mn sites. The model contains fermions and classical spins and hence we introduce a perturbative Monte Carlo scheme to increase the speed of our simulations.Comment: 17 pages, 24 figures, 2 table

Behaviour of the topological susceptibility in two colour QCD across the finite density transition

The behaviour of the topological susceptibility \chi in QCD with two colours and 8 flavours of quarks is studied at nonzero temperature on the lattice across the finite density transition. It is shown that the signal of \chi drops abruptly at a critical chemical potential \mu_c, much as it happens at the finite temperature and zero density transition. The Polyakov loop and the chiral condensate undergo their transitions at the same critical value \mu_c. At a value \mu_s of the chemical potential, called saturation point, which in our case satisfies \mu_s > \mu_c, Pauli blocking supervenes and consequently the theory becomes quenched.Comment: Latex file, 28 pages, 6 Figures, revised version with further study of Pauli blocking, phase diagram, physical units and the HMD algorithm. A few misprints corrected. Some references adde

Tuning Proton Conductivity in A Multifunctional Calcium Phosphonate Hybrid Framework

Multi-chelating phosphonate ligands are organic linkers alternative to polycarboxylates and other ligands providing synthetic access to a number of thermally- and chemically-stable MOFs [1]. Metal phosphonates are amenable for accessing suitable and highly conducting materials both by tuning structural features and post-synthesis treatment [2,3]. For instance, proton conductivity values in the order of 10−2 S cm–1 have been reported for several phosphonate-based compounds [4]. We report hereby the synthesis, structural characterization and proton conductivity of an open framework hybrid, Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H).(H2O)2].5H2O, that combines Ca2+ ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl)isophthalic acid. This compound was obtained by slow crystallization at ambient conditions at pH 3. Its complex pillared layered structure, solved by single crystal X-ray analysis, contains hydrophilic 1D channels filled with both water and acidic phosphonate and carboxylate groups creating a hydrogen-bonded network. Partial removal of the lattice water at 75 °C causes a monoclinic structural distortion but still retaining the initial conductivity properties (5.7x10-4 Sxcm-1). Exposure of the sample to ammonia vapor from a concentrated aqueous solution led to major structural changes resulting in a new layered material containing seven NH3 and sixteen H2O molecules per formula. This solid exhibits enhanced conductivity, reaching 6.6x10-3 S.cm-1, as measured at 98 % RH and T = 24 °C. Activation energies were between 0.23 and 0.40 eV, typical of a Grothuss mechanism of proton conduction.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. Proyecto Excelencia Junta de Andalucía, FQM-1656. MAT2010-15175