Li14Ln5[Si11N19O5]O2F2 with Ln = Ce, Nd-Representatives of a Family of Potential Lithium Ion Conductors

The isotypic layered oxonitridosilicates Li14Ln5[Si11N19O5]O2F2 (Ln = Ce, Nd) have been synthesized using Li as fluxing agent and crystallize in the orthorhombic space group Pmmn (Z = 2, Li14Ce5[Si11N19O5]O2F2: a = 17.178(3), b = 7.6500(15), c = 10.116(2) Å, R1 = 0.0409, wR2 = 0.0896; Li14Nd5 Si11N19O5]O2F2: a = 17.126(2), b = 7.6155 15), c = 10.123(2) Å, R1 = 0.0419, wR2 = 0.0929). The silicate layers consist of dreier and sechser rings interconnected via common corners, yielding an unprecedented silicate substructure. A topostructural analysis indicates possible 1D ion migration pathways between five crystallographic independent Li positions. The specific Li-ionic conductivity and its temperature dependence were determined by impedance spectroscopy as well as DC polarization/depolarization measurements. The ionic conductivity is on the order of 5 × 10−5 S/cm at 300°C, while the activation energy is 0.69 eV. Further adjustments of the defect chemistry (e.g., through doping)can make these compounds interesting candidates for novel oxonitridosilicate based ion conductors

Hydro-ionothermal synthesis of lanthanide-organic frameworks with 1,4-phenylenebis(methylene)diphosphonate

A synthetic approach combining hydrothermal and ionothermal (eutectic mixture of choline chloride and malonic acid) procedures is proposed that allowed the isolation of the first lanthanide-organic frameworks with residues of 1,4-phenylenebis(methylene)- diphosphonic acid (H4pmd), [Ln(Hpmd)(H2O)] (where Ln3+ ) Ce3+ and Pr3+), exhibiting an unprecedented trinodal topology with 3- and 8-connected nodes. The structural details were unveiled from single-crystal X-ray diffraction and the materials were characterized using standard techniques.FCT - POCI-PPCDT/QUI/58377/2004FEDER - POCIGrant - SFRH/BPD/9309/200

<i>CrystalGrower</i>: a generic computer program for Monte Carlo modelling of crystal growth.

From Europe PMC via Jisc Publications RouterHistory: ppub 2020-11-01, epub 2020-11-18Publication status: PublishedA Monte Carlo crystal growth simulation tool, CrystalGrower, is described which is able to simultaneously model both the crystal habit and nanoscopic surface topography of any crystal structure under conditions of variable supersaturation or at equilibrium. This tool has been developed in order to permit the rapid simulation of crystal surface maps generated by scanning probe microscopies in combination with overall crystal habit. As the simulation is based upon a coarse graining at the nanoscopic level features such as crystal rounding at low supersaturation or undersaturation conditions are also faithfully reproduced. CrystalGrower permits the incorporation of screw dislocations with arbitrary Burgers vectors and also the investigation of internal point defects in crystals. The effect of growth modifiers can be addressed by selective poisoning of specific growth sites. The tool is designed for those interested in understanding and controlling the outcome of crystal growth through a deeper comprehension of the key controlling experimental parameters

Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters

Three-dimensional lanthanide-organic frameworks formulated as (CH3)2NH2[Ln(pydc)2] · 1/2H2O [Ln3+ ) Eu3+ (1a) or Er3+ (1b); pydc2- corresponds to the diprotonated residue of 2,5-pyridinedicarboxylic acid (H2pydc)], [Er4(OH)4(pydc)4(H2O)3] ·H2O (2), and [PrIII 2PrIV 1.25O(OH)3(pydc)3] (3) have been isolated from typical solvothermal (1a and 1b in N,N-dimethylformamide - DMF) and hydrothermal (2 and 3) syntheses. Materials were characterized in the solid state using single-crystal X-ray diffraction, thermogravimetric analysis, vibrational spectroscopy (FT-IR and FT-Raman), electron microscopy, and CHN elemental analysis. While synthesis in DMF promotes the formation of centrosymmetric dimeric units, which act as building blocks in the construction of anionic ∞ 3{[Ln(pydc)2]-} frameworks having the channels filled by the charge-balancing (CH3)2NH2 + cations generated in situ by the solvolysis of DMF, the use of water as the solvent medium promotes clustering of the lanthanide centers: structures of 2 and 3 contain instead tetrameric [Er4(μ3-OH)4]8+ and hexameric |Pr6(μ3-O)2(μ3-OH)6| clusters which act as the building blocks of the networks, and are bridged by the H2-xpydcx- residues. It is demonstrated that this modular approach is reflected in the topological nature of the materials inducing 4-, 8-, and 14-connected uninodal networks (the nodes being the centers of gravity of the clusters) with topologies identical to those of diamond (family 1), and framework types bct (for 2) and bcu-x (for 3), respectively. The thermogravimetric studies of compound 3 further reveal a significant weight increase between ambient temperature and 450 °C with this being correlated with the uptake of oxygen from the surrounding environment by the praseodymium oxide inorganic core

Compressibility systematics of calcite-type borates : An experimental and theoretical structural study on ABO3 (A = Al, Sc, Fe and In)

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C , copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp4124259The structural properties of calcite-type orthoborates ABO(3) (A = Al, Fe, Sc, and In) have been investigated at high pressures up to 32 GPa. They were studied experimentally using synchrotron powder X-ray diffraction and theoretically by means of ab initio total-energy calculations. We found that the calcite-type structure remains stable up to the highest pressure explored in the four studied compounds. Experimental and calculated static geometries (unit-cell parameters and internal coordinates), bulk moduli, and their pressure derivatives are in good agreement. The compressibility along the c axis is roughly three times that along the a axis. Our data clearly indicate that the compressibility of borates is dominated by that of the [AO(6)] octahedral group and depends on the size of the trivalent A cations. An analysis of the relationship between isomorphic borates and carbonates is also presented, which points to the potentiality of considering borates as chemical analogues of the carbonate mineral family.This study was supported by the Spanish government MEC under Grant Nos.: MAT2010-21270-C04-01/03/04 and CTQ2009-14596-C02-01, by MALTA Consolider Ingenio 2010 Project (CSD2007-00045), by Generalitat Valenciana (GVA-ACOMP-2013-1012), and by the Vicerrectorado de Investigacion y Desarrollo of the Universidad Politecnica de Valencia (UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). We thank ALBA and Diamond synchrotrons for providing beamtime for the XRD experiments. A.M. and P.R-H. acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster. J.A.S. and B.G.-D. acknowledge Juan de la Cierva fellowship and FPI programs for financial support. We are gratefully indebted to Dr. Capponi and Dr. Diehl for supplying us single crystals of AlBO3 and FeBO3, respectively.Santamaría Pérez, D.; Gomis Hilario, O.; Sans, JÁ.; Ortiz, HM.; Vegas, Á.; Errandonea, D.; Ruiz-Fuertes, J.... (2014). Compressibility systematics of calcite-type borates : An experimental and theoretical structural study on ABO3 (A = Al, Sc, Fe and In). Journal of Physical Chemistry C. 118(8):4354-4361. https://doi.org/10.1021/jp4124259S43544361118

Synthesis of ‘unfeasible’ zeolites

R.E.M. thanks the Royal Society and the E.P.S.R.C. (Grants EP/L014475/1, EP/K025112/1 and EP/K005499/1) for funding work in this area. J.Č. and P.N. acknowledge the Czech Science Foundation for the project of the Centre of Excellence (P106/12/G015) and the European Union Seventh Framework Programme (FP7/ 2007-­‐2013) under grant agreement n°604307. The research leading to these results has received funding from the European Union Seventh Framework Programme under Grant Agreement 312483 – ESTEEM2 (Integrated Infrastructure Initiative–I3). We thank Professor Wuzong Zhou and Dr. Fengjiao Yu for their expertise in TEM and Daniel Dawson for help with NMR.Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum - why have only so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such 'unfeasible' zeolites, IPC-9 and IPC-10, through the assembly-disassembly-organization-reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications.PostprintPeer reviewe

Topological insights in polynuclear Ni/Na coordination clusters derived from a schiff base ligand

This article presents the syntheses, crystal structures, topological features and magnetic properties of two NiII/NaI coordination clusters (CCs) formulated [NiII3Na(L1)3(HL1 (MeOH)2] (1) and [NiII6Na(L1)5(CO3)(MeO (MeOH)3(H2O)3]·4(MeOH) 2(H2O) [2 4(MeOH) 2(H2O)] where H2L1 is the semi rigid Schiff base ligand (E)-2-(2-hydroxy-3 methoxybenzylideneamino)-phenol). Compound 1 possesses a rare NiII3NaI cubane (3M4-1) topology and compound 2 is the first example in polynuclear Ni/Na chemistry that exhibits a 2,3,4M7-1 topology

Magnetic and Photoluminescent Sensors Based on Metal-Organic Frameworks Built up from 2-aminoisonicotinate

Red Guipuzcoana de Ciencia, Tecnologia e Innovacion OF218/2018 University of Basque Country GIU 17/13 Basque Government IT1005-16 IT1291-19 IT1310-19 Junta de Andalucia FQM-394 Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) PGC2018-102052-A-C22 PGC2018-102052-B-C21 MAT2016-75883-C2-1-P European Union (EU) ESFIn this work, three isostructural metal-organic frameworks based on frst row transition metal ions and 2-aminoisonicotinate (2ain) ligands, namely, {[M(μ-2ain)2]·DMF}n [MII=Co (1), Ni (2), Zn (3)], are evaluated for their sensing capacity of various solvents and metal ions by monitoring the modulation of their magnetic and photoluminescence properties. The crystal structure consists of an open diamond-like topological 3D framework that leaves huge voids, which allows crystallizing two-fold interpenetrated architecture that still retains large porosity. Magnetic measurements performed on 1 reveal the occurrence of feld-induced spin-glass behaviour characterized by a frequency-independent relaxation. Solvent-exchange experiments lead successfully to the replacement of lattice molecules by DMSO and MeOH, which, on its part, show dominating SIM behaviour with low blocking temperatures but substantially high energy barriers for the reversal of the magnetization. Photoluminescence studied at variable temperature on compound 3 show its capacity to provide bright blue emission under UV excitation, which proceeds through a ligand-centred charge transfer mechanism as confrmed by timedependent DFT calculations. Turn-of and/or shift of the emission is observed for suspensions of 3 in diferent solvents and aqueous solutions containing metal ions