Open-Framework Solids with Diamond-Like Structures Prepared from Clusters and Metal-Organic Building Blocks

1994 ◽  
Vol 371 ◽  
Author(s):  
Omar M. Yaghi ◽  
D. A. Richardson ◽  
G. Li ◽  
C. E. Davis ◽  
T. L. Groy
Keyword(s):  
Metal Ion ◽  
Building Blocks ◽  
Diamond Structure ◽  
Tetrahedral Cluster ◽  
X Ray ◽  
Open Framework ◽  
X Ray Crystallography ◽  
Metal Organic ◽  
Channel Systems ◽  
Cu And Zn

AbstractThe tetrahedral cluster Ge4S104- and the rodlike ligand 4,4′-bipyridine are utilized in addition copolymerization reactions with the metal (II) ions of Mn, Fe, Co, Cu, and Zn in the preparation of 3-D open-framework solids, MxCol-xGe4S10-2(CH3)4N (x = 0.86, M = Mn; x = 1, M = Mn, Fe, Co, and Zn), 1, and Cu(4,4′-bpy)2. PF6, 2, having diamond-like structures. These structures are viewed in terms of the cubic diamond structure, where the carbon atoms have been replaced by either a cluster or a metal ion and the C-C bond by a sulfide or the 4,4′-bpy. These compounds have been fully characterized by single crystal x-ray crystallography and their composition was confirmed by elemental analysis; they contain 3-D channel systems where cations or anions reside to balance the charge on the framework.

Synthesis and Structure of a Metal-Organic Solid Having the Cadmium(II) Sulfate Net

1996 ◽  
Vol 453 ◽  
Author(s):  
O. M. Yaghi ◽  
Hailian Li ◽  
M. O'Keeffe
Keyword(s):  
Single Crystal ◽  
Building Blocks ◽  
Relative Orientation ◽  
X Ray ◽  
Open Framework ◽  
Elemental Microanalysis ◽  
Organic Solid ◽  
Metal Organic

AbstractReaction of silver(I) nitrate and hexamethylenetetramine (HMTA) gives crystals of Ag2(HMTA)(NO3)2, which was formulated by elemental microanalysis and a single crystal x-ray study. Its Ag2(HMTA) open-framework is the first example of a decorated CdSO4net. The relative orientation of the tetrahedral HMTA building blocks in this structure point to numerous opportunities toward constructing novel chiral and polar porous frameworks.

A New POM-Based Supramolecular Compound: Synthesis, Structure and Adsorptive Property of [Cu(phen)2]3[W6O19]

2014 ◽  
Vol 919-921 ◽  
pp. 2013-2016 ◽  
Author(s):  
Ya Bing Liu ◽  
Hong Jie Wang ◽  
Hong Kai Zhao
Keyword(s):  
Three Dimensional ◽  
Building Blocks ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Hybrid Compound ◽  
Adsorptive Property ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Compound Synthesis ◽  
Metal Organic

A POM - based organice - inorganic hybrid compound with the chemical formula of[Cu (phen)2]3[W6O19] (phen = 1,10-phenanthroline) (1) has been hydrothermally synthesized andstructurally characterized by the elemental analysis, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space groupC2/c witha=18.319(4) Å,b= 17.311(4) Å,c= 22.248(4) Å,β= 112.40(3) o,V= 6523(2) Å3,Z= 4, R1= 0.0448, andwR2=0.1218. Compound 1 consists of the [W6O19]3-building blocks and [Cu (phen)2]+metal organic cationic moieties, which are packed together via the extensive hydrogen-bonding interactions to form a three-dimensional supramolecular framework. The adsorption of methylene blue (MB) under UV irradiation with 1 as the heterogeneous adsorbent has been investigated, showing a good adsorptive property of 1 for MB degradation.

scholarly journals Compressibility Studies of Zirconium Based Metal-Organic Frameworks

2014 ◽  
Vol 70 (a1) ◽  
pp. C157-C157
Author(s):  
Claire Hobday ◽  
Stephen Moggach ◽  
Carole Morrison ◽  
Tina Duren ◽  
Ross Forgan
Keyword(s):  
High Pressure ◽  
Mechanical Stability ◽  
Metal Organic Frameworks ◽  
External Pressure ◽  
X Ray Diffraction ◽  
X Ray ◽  
X Ray Crystallography ◽  
Pressure Medium ◽  
Metal Organic ◽  
University Of Oslo

Metal-organic frameworks (MOFs) are a well-studied class of porous materials with the potential to be used in many applications such as gas storage and catalysis.[1] UiO-67 (UiO = University of Oslo), a MOF built from zirconium oxide units connected with 4,4-biphenyldicarboxylate (BDC) linkers, forms a face centred cubic structure. Zirconium has a high affinity towards oxygen ligands making these bridges very strong, resulting in UiO-based MOFs having high chemical and thermal stability compared to other MOF structures. Moreover, UiO-67 has become popular in engineering studies due to its high mechanical stability.[2] Using high pressure x-ray crystallography we can exert MOFs to GPa pressures, experimentally exploring the mechanical stability of MOFs to external pressure. By immersing the crystal in a hydrostatic medium, pressure is applied evenly to the crystal. On surrounding a porous MOF with a hydrostatic medium composed of small molecules (e.g. methanol), the medium can penetrate the MOF, resulting in medium-dependant compression. On compressing MOF-5 (Zn4O(BDC)3) using diethylformamide as a penetrating medium, the framework was shown to have an increased resistance to compression, becoming amorphous several orders of magnitude higher in pressure than observed on grinding the sample.[3] Here we present a high-pressure x-ray diffraction study on the UiO-based MOF UiO-67, and several new synthesised derivatives built from same metal node but with altered organic linkers, allowing us to study in a systematic way, the mechanical stability of the MOF, and its pressure dependence on both the linker, and pressure medium.

scholarly journals In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

2020 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Nucleation And Growth ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rate Determining Step ◽  
Wide Range ◽  
Metal Organic

We report on the results of a thorough <i>in situ</i> synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds <i>in situ</i> in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO<sub>3</sub>) and amount of the coordination modulator acetic acid (AcOH). When only HNO<sub>3</sub> is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO<sub>3</sub>, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO<sub>3</sub> slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO<sub>3</sub> favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO<sub>3</sub>. Based on these <i>in situ</i> results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

Synthesis and characterization of new tetra-substituted porphyrins with exo-donor carboxylic groups as building blocks for supramolecular architectures: Catalytic and structural studies of their metalated derivatives

2010 ◽  
Vol 14 (09) ◽  
pp. 804-814 ◽  
Author(s):  
Lucia Carlucci ◽  
Gianfranco Ciani ◽  
Simona Maggini ◽  
Davide M. Proserpio ◽  
Fabio Ragaini ◽  
...  
Keyword(s):  
Building Blocks ◽  
Supramolecular Organization ◽  
Silver Complexes ◽  
Structural Studies ◽  
Polymeric Compound ◽  
X Ray ◽  
X Ray Crystallography ◽  
Supramolecular Architectures ◽  
Carboxylic Groups

We report herein the synthesis of the porphyrins 5,10,15,20-tetrakis(4-carboxybiphenyl)-porphyrin (H2TCBP) and 5,10,15,20-tetrakis(4-carboxy-2,6-dimethylbiphenyl)porphyrin (H2TCDMBP) bearing diphenyl units on meso-positions, and of their cobalt and silver derivatives. The silver complexes of H2TCDMBP and of H2TCPP ( H2TCPP = 5 ,10,15,20-tetrakis(4-carboxyphenyl)porphyrin) were investigated by X-ray crystallography and their supramolecular organization elucidated. Co(TCBP) was reacted with copper formate, yielding a polymeric compound that showed a catalytic activity in the benzylic amination of hydrocarbons using arylazide as aminating agent.

scholarly journals X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

2017 ◽  
Vol 375 (2084) ◽  
pp. 20160028 ◽  
Author(s):  
Michael T. Huxley ◽  
Campbell J. Coghlan ◽  
Witold M. Bloch ◽  
Alexandre Burgun ◽  
Christian J. Doonan ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Metal Organic Frameworks ◽  
Void Space ◽  
X Ray ◽  
X Ray Crystallography ◽  
Metal Nitrates ◽  
Metal Organic

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.

scholarly journals Nickel Salicylaldoxime-Based Coordination Polymer as a Cathode for Lithium-Ion Batteries

Energies ◽  
2020 ◽  
Vol 13 (10) ◽  
pp. 2480
Author(s):  
Evgenii V. Beletskii ◽  
Daniil A. Lukyanov ◽  
Petr S. Vlasov ◽  
Andrei N. Yankin ◽  
Arslan B. Atangulov ◽  
...  
Keyword(s):  
Energy Storage ◽  
Cathode Materials ◽  
Lithium Ion ◽  
Building Blocks ◽  
Organic Polymer ◽  
Galvanostatic Charge ◽  
X Ray ◽  
Storage Performance ◽  
Redox Active ◽  
Metal Organic

Conjugated coordination polymers attract attention as materials for electrochemical energy storage, mostly as cathode materials for supercapacitors. Faradaic capacity may be introduced to such materials using redox-active building blocks, metals, or ligands. Using this strategy, a novel hybrid cathode material was developed based on a Ni2+ metal-organic polymer. The proposed material, in addition to double-layer capacitance, shows high pseudocapacitance, which arises from the contributions of both the metal center and ligand. A tailoring strategy in the ligand design allows us to minimize the molecular weight of the ligand, which increases its gravimetric energy. According to computational results, the ligand makes the prevailing contribution to the pseudocapacitance of the material. Different approaches to metal–organic polymer (MOP) synthesis were implemented, and the obtained materials were examined by FTIR, Raman spectroscopy, powder XRD, SEM/EDX (energy-dispersive X-ray spectroscopy), TEM, and thermal analysis. Energy-storage performance was comparatively studied with cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). As a result, materials with an excellent discharge capacity were obtained, reaching the gravimetric energy density of common inorganic cathode materials.

scholarly journals Two step formation of metal aggregates by surface X-ray radiolysis under Langmuir monolayers: 2D followed by 3D growth

2015 ◽  
Vol 6 ◽  
pp. 2406-2411
Author(s):  
Smita Mukherjee ◽  
Marie-Claude Fauré ◽  
Michel Goldmann ◽  
Philippe Fontaine
Keyword(s):  
Metal Ion ◽  
Langmuir Monolayers ◽  
Langmuir Monolayer ◽  
Silver Layer ◽  
Silver Clusters ◽  
Organic Layer ◽  
Angle Of Incidence ◽  
X Ray ◽  
Second Growth ◽  
Metal Organic

In order to form a nanostructured metallic layer below a Langmuir monolayer, radiolysis synthesis was carried out in an adapted geometry that we call surface X-ray radiolysis. In this procedure, an X-ray beam produced by a synchrotron beamline intercepts the surface of an aqueous metal-ion solution covered by a Langmuir monolayer at an angle of incidence below the critical angle for total internal reflection. Underneath the organic layer, the X-ray beam induces the radiolytic synthesis of a nanostructured metal–organic layer whose ultrathin thickness is defined by the vertical X-ray penetration depth. We have shown that increasing the X-ray flux on the surface, which considerably enhances the kinetics of the silver layer formation, results in a second growth regime of silver nanocrystals. Here the formation of the oriented thin layer is followed by the appearance of a 3D powder of silver clusters.

Metalloligand Strategies for Assembling Heteronuclear Nanocages – Recent Developments

2019 ◽  
Vol 72 (10) ◽  
pp. 731 ◽  
Author(s):  
Feng Li ◽  
Leonard F. Lindoy
Keyword(s):  
Structural Properties ◽  
Metal Ion ◽  
Rational Design ◽  
Building Blocks ◽  
Structural Elements ◽  
Present Discussion ◽  
The Past ◽  
Recent Developments ◽  
Metal Organic ◽  
Multifunctional Ligand

The use of metalloligands as building blocks for the assembly of metallo-organic cages has received increasing attention over the past two decades or so. In part, the popularity of this approach reflects its stepwise nature that lends itself to the predesigned construction of metallocages and especially heteronuclear metallocages. The focus of the present discussion is on the use of metalloligands for the construction of discrete polyhedral cages, very often incorporating heterometal ions as structural elements. The metalloligand approach uses metal-bound multifunctional ligand building blocks that display predesigned structural properties for coordination to a second metal ion such that the rational design and construction of both homo- and heteronuclear metal–organic cages are facilitated. The present review covers published literature in the area from early 2015 to early 2019.

Preparation and characterization of Tl(1,2-C2H4Cl2)B(OTeF5)4: a metal complex of a least coordinating solvent and a least coordinating anion

1992 ◽  
Vol 70 (3) ◽  
pp. 726-731 ◽  
Author(s):  
Paul K. Hurlburt ◽  
Oren P. Anderson ◽  
Steven H. Strauss
Keyword(s):  
Metal Ion ◽  
Chelate Ring ◽  
Ion Solvation ◽  
Crystalline Compound ◽  
Triclinic Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Solid Salt ◽  
Solvent Metal

Addition of B(OTeF5)3 to TIOTeF5 in the weakly coordinating solvents dichloromethane, 1,2-dichloroethane, and 1,1,2-trichlorotrifluoroethane produces solutions of M(solv)x+B(OTeF5)4−. When the solvent was 1,2-dichloroethane, the crystalline compound Tl(1,2-C2H4Cl2)B(OTeF5)4 was isolated and studied by X-ray crystallography: triclinic, space group [Formula: see text], a = 9.221 (4), b = 11.396(5), c = 12.538 (4) Å, α = 110.75 (3)°, β = 101.72(3)°, γ = 99.74 (3)°, Z = 2, T = −116 °C. The Tl(1,2-C2H4Cl2)+ cation contains a five-membered chelate ring with Tl—Cl distances of 3.138 (4) and 3.179 (3) Å. The metal ion is weakly bonded to four B(OTeF5)4− counterions, with nine Tl—F interactions that range from 2.950 (5) to 3.981 (8) Å. When the solvent is dichloromethane or 1,1,2-trichlorotrifluoroethane, only the unsolvated solid salt TlB(OTeF5)4 can be isolated by crystallization. This salt is thermally unstable, slowly forming TlOTeF5 and volatile B(OTeF5)3. Keywords: noncoordinating anion, noncoordinating solvent, metal ion solvation.

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