Effect of Mixing of Metal Cations on the Topology of Metal Oxide Networks

Livage, Carine; Forster, Paul M.; Guillou, Nathalie; Tafoya, Maya M.; Cheetham, Anthony K.; Férey, Gérard

doi:10.1002/anie.200700247

Cited by 52 publications

(21 citation statements)

References 38 publications

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“…For MOCNs 1-4, it is likely that subtle alterations in the binodal cubical vertices/ square-planar connectivity between the trimetallic clusters and the btec ligands resulted in differences in supramolecular environments and lowered cell symmetry to a primitive monoclinic space group for the last three. The nature (d-electron configuration) of the transition metal ions (Co II , Ni II ) herein may have a significant influence on the final connectivity, [31] whereas alkali metal ions (K + , Cs + ) seem to have only a minor effect, but act as templates. This difference most likely is due to both the inherent tendency for coordination of transition metal ions (octahedral for Co II and square-planar for Ni II ) [31] and the size of the alkali metal ions (10 3 for K + and 19 3 for Cs + ).…”

Section: Resultsmentioning

confidence: 99%

“…The nature (d-electron configuration) of the transition metal ions (Co II , Ni II ) herein may have a significant influence on the final connectivity, [31] whereas alkali metal ions (K + , Cs + ) seem to have only a minor effect, but act as templates. This difference most likely is due to both the inherent tendency for coordination of transition metal ions (octahedral for Co II and square-planar for Ni II ) [31] and the size of the alkali metal ions (10 3 for K + and 19 3 for Cs + ). [32] For cobalt-containing metal-organic coordination networks, a regular architecture is favored in the presence www.chemeurj.org of small potassium ions.…”

Section: Resultsmentioning

confidence: 99%

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Alkali Metal Cation (K⁺, Cs⁺) Induced Dissolution/Reorganization of Porous Metal Carboxylate Coordination Networks in Water

Ding

Wen

et al. 2009

Chemistry A European J

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Porous metal-organic coordination networks (MOCNs) {A(2)[M(3)(btec)(2)(H(2)O)(4)]}(n) (1, A=K, M=Co; 2, A=K, M=Ni; 3, A=Cs, M=Co; and 4, A=Cs, M=Ni; btec=benzene-1,2,4,5-tetracarboxylate) with nearly identical structural features were hydrothermally prepared. These compounds adopt (4,8)-connected scu nets but exhibit subtle differences in the topology of the final three-dimensional architectures. Compound 1 has a regular net with the largest solvent void (21.1 %), while the nets of the other three (2-4) are slightly distorted from a regular shape and have malformed pores with smaller solvent voids (5.4-11.4 %). Likely, the different supramolecular environments among 1-4 subtly depend on the eight-connected binodal cubical vertices/four-connected square-planar connectivity between the trimetallic clusters and the btec ligands. Cobalt species 3 dissolved in an aqueous solution of KCl, and then reorganized to form 1 at ambient temperature. Interestingly, under similar conditions, 1 dissolved and then was regenerated to give the same structure. Nickel species 2 and 4 also underwent a dissolution/reorganization process in an aqueous solution of KCl to afford new metal-carboxylate product {K(2)[Ni(3)(btec)(2)(H(2)O)(4)]}(n) (2'). This compound forms a (4,8)-connected scu net with regular pores, which is isostructural and isomorphous with 1, and is a supramolecular isomer of 2. Similarly, in an aqueous solution of CsCl, 1-4 were converted to 1D zigzag chain structures {Cs(2)[M(btec)(H(2)O)(4)]}(n) (5, M=Co; 6, M=Ni) that enlarged to hydrogen-bonded 3D porous supramolecular networks. Remarkable, reversible alkali metal cation induced structural transformations between 1 and 5 occurred via dissolution/reorganization processes. Thermogravimetric analyses showed that these metal-carboxylate species have high thermal stability (T>300 degrees C).

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Alkali Metal Cation (K⁺, Cs⁺) Induced Dissolution/Reorganization of Porous Metal Carboxylate Coordination Networks in Water

Ding

Wen

et al. 2009

Chemistry A European J

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“…[23,[38][39][40][41] MM-MOFs in which two different metals are presented in acertain proportion range have been reported to be prepared using synthetic procedures common in MOF synthesis,s uch as conventional heating and solvothermal procedures. [17,[42][43][44][45][46][47][48][49] Depending on the synthesis conditions and the nature and proportion of the various metal precursors the resulting MM-MOF can be derived from the thermodynamic or kinetic control and this may influence the distribution and location of the metals. Considering the possible differences,the synthetic procedures should screen av ariety of conditions,d etermining the influence of various parameters in the final MM-MOF.…”

Section: One-pot Synthesis Of Mm-mofsusing Mixtures Of Different Metamentioning

confidence: 99%

Mixed‐Metal MOFs: Unique Opportunities in Metal–Organic Framework (MOF) Functionality and Design

et al. 2019

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MOFs are synthesized following al arge variety of procedures,i ncluding solvo/hydro thermal methods,s low diffusion, conventional heating, slow evaporation, mechanochemical, and sonochemical. [28][29][30][31][32] Several of these synthetic Mixed-metal metal-organic frameworks (MM-MOFs) can be considered to be those MOFs having two different metals anywhere in the structure.H erein we summarizethe various strategies for the preparation of MM-MOFs and some of their applications in adsorption, gas separation, and catalysis.I ti sshown that compared to homometallic MOFs,MM-MOFs bring about the opportunity to take advantage of the complexity and the synergism derived from the presence of different metal ions in the structure of MOFs.This is reflected in as uperior performance and even stability of MM-MOFs respect to related single-metal MOFs.Emphasis is made on the use of MM-MOFs as catalysts for tandem reactions.

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“…5,[7][8][9] Incorporating two or more different cations or ligands into a framework allows the crystal structure, and thus the functional properties of such materials, to be tailored to particular applications. [10][11][12] It has been shown that cation doping in frameworks can lead to either the formation of solid solutions 11 or a sequence of phase transitions with changing composition, 12 similarly to purely inorganic materials. The effect, however, of mixing two ligands in a framework is less clear, especially since most compounds reported to date feature two very different ligands e.g.…”

Section: Introductionmentioning

confidence: 99%

Structures and magnetic properties of Mn and Co inorganic–organic frameworks with mixed linear dicarboxylate ligands

et al. 2012

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The structures and magnetic properties of two transition metal frameworks that feature a mixture of two linear dicarboxylate ligands are reported. Compoundscontain a mixture of succinate and adipate ligands but adopt significantly different structures. Compound 1 features layers of MnO 6 dimers, intraconnected by carboxylate groups, with neighbouring dimers connected to each other via the adipate ligands in one direction and succinate ligands in the other. Extensive hydrogen bonding in the third dimension provides the main force holding layers together. Framework 2 has inorganic layers of CoO 6 octahedra arranged into rings of 14 members each, with adipate ligands providing inter-layer connectivity. The structures of these two compounds are compared to Mn and Co dicarboxylate frameworks containing only one type of organic ligand, including Co(C 6 H 8 O 4 ), compound 3, whose structure is reported in this work for the first time; they are found to be significantly different from those that form under similar conditions. Both compounds order magnetically near 2 K. Compound 1 is an antiferromagnet, in which the intra-dimer coupling dominates the magnetic behaviour, while framework 2 is most likely a canted antiferromagnet. Both compounds undergo magnetic phase transitions with increasing applied magnetic fields, at 14 kOe and 0.35 kOe in 1 and 2, respectively. The transition in the Mn compound is a simple spin flop but in the Co compound the suppression of the long range ordered state is also accompanied by the elimination of the ferromagnetic component of its magnetic interactions.

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Effect of Mixing of Metal Cations on the Topology of Metal Oxide Networks

Cited by 52 publications

References 38 publications

Alkali Metal Cation (K⁺, Cs⁺) Induced Dissolution/Reorganization of Porous Metal Carboxylate Coordination Networks in Water

Alkali Metal Cation (K⁺, Cs⁺) Induced Dissolution/Reorganization of Porous Metal Carboxylate Coordination Networks in Water

Mixed‐Metal MOFs: Unique Opportunities in Metal–Organic Framework (MOF) Functionality and Design

Structures and magnetic properties of Mn and Co inorganic–organic frameworks with mixed linear dicarboxylate ligands

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Effect of Mixing of Metal Cations on the Topology of Metal Oxide Networks

Cited by 52 publications

References 38 publications

Alkali Metal Cation (K+, Cs+) Induced Dissolution/Reorganization of Porous Metal Carboxylate Coordination Networks in Water

Alkali Metal Cation (K+, Cs+) Induced Dissolution/Reorganization of Porous Metal Carboxylate Coordination Networks in Water

Mixed‐Metal MOFs: Unique Opportunities in Metal–Organic Framework (MOF) Functionality and Design

Structures and magnetic properties of Mn and Co inorganic–organic frameworks with mixed linear dicarboxylate ligands

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Alkali Metal Cation (K⁺, Cs⁺) Induced Dissolution/Reorganization of Porous Metal Carboxylate Coordination Networks in Water

Alkali Metal Cation (K⁺, Cs⁺) Induced Dissolution/Reorganization of Porous Metal Carboxylate Coordination Networks in Water