Hybrid Open Frameworks Research Articles

Heterometallic Hybrid Open Frameworks: Synthesis and Application for Selective Detection of Nitro Explosives

Three inorganic–organic hybrid open frameworks based on heterometallic cluster building blocks, formulated as Cd2Cs3(NDC)3(OAc)(DMA)2(H2O) (1), [NH2(CH3)2]2·Cd2Mg(NDC)4·Gx (2), and [NH2(CH3)2]3·Cd2K(NDC)4·Gx (3) (H2NDC = 2,6-naphthalenedicarboxylic acid, G = guest solvent molecule), were synthesized under solvothermal conditions. Compound 1 has a pillared layered structure featuring inorganic hcb-type layers with 14-ring windows and simultaneously exhibits a 3D open framework constructed from two types of heterometallic clusters, i.e., {Cd2Cs2O18} and {CdCs4O18}, and the NDC2– ligand. Compounds 2 and 3 are constructed from linear trinuclear {Cd2M} (M = Mg and K) building blocks and the NDC2– ligand, featuring 1D square channels with rld-z topology. Of the three heterometallic hybrid open frameworks, compounds 1 and 2 exhibited strong blue-light emission due to the presence of fluorescent organic ligands in the anionic frameworks, and more importantly, their strong fluorescence could be selectively quenche...

Organic-inorganic hybrid three-dimensional metal sulfite-oxalates with honeycomb-like structures.

The crystallographic signatures and characterization of two novel mixed metal hybrid open-frameworks [Na2Mn2(C2O4)(SO3)2(H2O)2] 1 and [NaEu(C2O4)(SO3)(H2O)3] 2 are reported for the first time; they are synthesized under hydrothermal conditions to generate 3D assemblies and honeycomb-like structures. They were further characterized by complementary techniques like PXRD, TGA and DSC. The magnetic properties of 1 show antiferromagnetic interactions between the metal centers and compound 2 shows good photoluminescence properties.

Room Temperature Synthesized Hybrid Open Frameworks for Li-Ion Battery Cathodes

Li-ion batteries (LIBs) have been the most promising battery technology owing to their large energy density, environmental friendliness and design flexibility. LIBs have been dominating the rechargeable battery market fue to their advantages and they found application in various electonic gadgets. Large scale utilization of LIBs is anticipated in the near future for efficient utilization of renewable energy as there is gap between energy supply and demand. As solar radiation is available during daytime, the peak energy demand is at night. In addition, LIBs are expected to push forward the production of eco-friendly transportation such as electric vehicles (EVs) and hybrid electric vehicles (HEVs). Transformation from conventional vehicles to EVs are mainly hindered by the high upfront price of the EVs which are mainly due to the high cost of the battery packs used to power these vehicles. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, a Graphene/MOPOF (Metal Organophosphate Open Framework) [1-3] nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that does not require any expensive post-synthetic treatments at high temperature in inert atmospheres like Ar/Ar-H2. These open frameworks has a layered structure with each layer made of metal phosphate cross-linked by oxalate. Presence of alkali ions in the interlayer space with a redox system helpes in the reversible extraction of them, making it a feasible cathode material. Though the pristine material undergoes reversible lithium storage, there was capacity fading. Enhanced lithium cycling with minimal capacity fading was witnessed with the graphene nanocomposite owing to the increased electronic conductivity and enhanced Li diffusivity. Stable reversible capacity of ~100 mAh g-1 were obtained. Refereces A. Shahul Hameed, M. V. Reddy, M. Nagarathinam, Tomče Runčevski, Robert E Dinnebier, Stefan Adams, B. V. R. Chowdari and Jagadese J. Vittal, Sci. Rep., 2015, 5, 16270. A. Shahul Hameed, M. Nagarathinam, Martin Schreyer, M. V. Reddy, B. V. R. Chowdari and Jagadese J. Vittal, J. Mater. Chem. A, 2013, 1, 5721-5726.M. Nagarathinam, K. Saravanan, E. J. H. Phua, M. V. Reddy,B. V. R. Chowdari and J. J. Vittal, Angew. Chem., Int. Ed., 2012, 51, 5866–5870.

Chemical structure, network topology, and porosity effects on the mechanical properties of Zeolitic Imidazolate Frameworks

The mechanical properties of seven zeolitic imidazolate frameworks (ZIFs) based on five unique network topologies have been systematically characterized by single-crystal nanoindentation studies. We demonstrate that the elastic properties of ZIF crystal structures are strongly correlated to the framework density and the underlying porosity. For the systems considered here, the elastic modulus was found to range from 3 to 10 GPa, whereas the hardness property lies between 300 MPa and 1.1 GPa. Notably, these properties are superior to those of other metal-organic frameworks (MOFs), such as MOF-5. In substituted imidazolate frameworks, our results show that their mechanical properties are mainly governed by the rigidity and bulkiness of the substituted organic linkages. The framework topology and the intricate pore morphology can also influence the degree of mechanical anisotropy. Our findings present the previously undescribed structure-mechanical property relationships pertaining to hybrid open frameworks that are important for the design and application of new MOF materials.

Hybrid 2D and 3D Frameworks Based on ϵ‐Keggin Polyoxometallates: Experiment and Simulation

AbstractThe ϵ‐Keggin polyoxomolybdate {ϵ‐PMoV8MoVI4O40–x(OH)xM4} is a versatile building unit, with M being either a ZnII or a LaIII capping ion located at the vertices of a slightly distorted tetrahedron. The charge of the Keggin unit depends on the number of protonated oxo bridging ligands, which has been shown to vary from 0 to 5. The Keggin entity can thus be either an anion (M = Zn, x = 0) or a cation (M = La, x = 3–5). The Zn derivative has been generated in situ by hydrothermal synthesis and forms a 2D material built from the connection of the cations by 4,4'‐bipyridine ligands linked to the capping ZnII ions. The reaction of the chloride salt of the La derivative with di‐, tri‐ and tetrasubstituted benzenecarboxylate ligands has allowed us to isolate 2D and 3D materials. The 3D materials seem to be the first examples of hybrid open frameworks based on Keggin building blocks. The 3D framework built from the connection of ϵ‐Keggin units by trimesate ions exhibits tunnels filled only by water molecules, which can be partly removed and reintroduced at room temperature. Besides these experimental results, simulation has allowed us to generate two virtual hybrid structures derived from those of known silicates by replacing the Si ions by hypothetical ϵ‐Keggin cations and the O‐bridging ligands by terephthalate ions, thus showing that 3D frameworks with large pores can be envisioned in the chemistry of hybrid organic–inorganic materials based on ϵ‐Keggin units and motivating further experimental investigations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Hybrid open frameworks: Hydrothermal synthesis and structure determination of MIL-33: a new vanadomethylendiphosphonate intercalating potassium cations

The hydrothermal synthesis and the ab initio structure determination from powder data of K2(VVO2)4(VIVO){O3P–CH2–PO3}2–xH2O (x=4) or MIL-33 are presented. MIL-33 crystallizes in the monoclinic system [space group C2/m (No. 12)] with lattice parameters a=4.8716(4) Å, b=14.614(1) Å, c=15.825(1) Å, β=94.06(1) Å, V=1123.8(2) Å3, Z=2. MIL-33 is a mixed valence VIV/VV=1/4 vanadodiphosphonate. Its layered structure shows some potassium cations located both between the hybrid layers and in the eight-membered windows of the latter.

Hybrid Open-frameworks: structure determinations and ferromagnetism of MIL-41 or (V(IV)O)2M(II)(H2O)4{HO3PCH2PO3}2 · 2H2O (M=Mn, Co, Ni, Zn): four mixed metallomethylendiphosphonates hydrothermally synthesized by using pre-assembled building units

MIL-41 or (V(IV)O)2M(II)(H2O)4{HO3PCH2PO3}2 · 2H2O was hydrothermally synthesized at 443 K with M(II)=Mn, Co, Ni, Zn. The structures of the four compounds were solved by single crystal X-ray diffraction in the noncentrosymmetric orthorhombic space group Fdd2 (no. 43). The lattice parameters of the Mn compound are a=22.0237(3) Å, b=22.3722(4) Å, c=7.2962(2) Å, V=3595.0(1) Å3, Z=8 and the reliability factors R1=0.0352, wR2=0.0840 for 2142 reflections with I≥2σ(I). The structure of MIL-41 is two-dimensional (2-D) with layers built from mixed vanadomethylendiphosphonate chains linked by MO2(H2O)4 octahedra. These solids are ferromagnetic below 5 K due to dipolar interactions.

Hybrid open-frameworks. Hydrothermal synthesis and structure determination of MIL-40 or V IV O(H 2 O){HO 3 P–CH 2 –(C 6 H 4 )–CH 2 –PO 3 H}: a lamellar vanadodiphosphonate prepared with p -xylendiphosphonic acid

Abstract VIVO(H2O){HO3P–CH2–(C6H4)–CH2–PO3H} labelled MIL-40 is a hybrid organic–inorganic compound whose bidimensional structure is built up from (VIV=O)2+ vanadyl groups and p-xylendiphosphonate units. MIL-40 was hydrothermally prepared at 443 K and its structure solved from single crystal X-ray diffraction data. It is triclinic (space group P 1 , n° 2) with lattice parameters a = 7.255 8(8) A, b = 7.573 9(8) A, c = 11.493(1) A, α = 93.230(2) °, β = 103.018(2) °, γ = 96.871(2) °, V = 608.7(1) A3, Z = 2, R1(F0) = 0.091 1, wR2(F02) = 0.189 6 for 2 843 unique reflections with I ≥ 2 σ(I). Its thermal decomposition is investigated.

Hybrid open frameworks: synthesis, structure and thermal behaviour of MIL‐26, a new three-dimensional vanadium(iv) ethylcarboxyphosphonate Na[VIVO(O3P(CH2)2CO2)]·2H2O

Na[VIVO(O3P(CH2)2CO2)]·2H2O, MIL-26, was synthesized hydrothermally at 453 K for 24 h under autogenous pressure. Its three-dimensional open structure was determined by single crystal X-ray diffraction. MIL-26 is monoclinic (space group P21, no. 4) with cell parameters at 293 K: a = 6.4041(3), b = 17.6252(8), c = 7.7271(3) A, β = 95.586(2)°, Z = 4, V = 868.04(7) A3. Its framework is constituted of double chains based on isolated VIVO6 octahedra linked by PO3C tetrahedral groups of the [O3PCH2CH2CO2]3− organic cations. At the other end of each organic chain, CO2− chelates a VO6 octahedron of a neighbouring chain. Each double chain is connected to four others by these organic chains thus defining elliptical channels along [100] in which water molecules and Na+ cations are located.

Hybrid open-frameworks: synthesis and structures of four vanado-alkyldiphosphonates with occluded potassium cations

The ternary systems KVO3:H2O3P(CH2)nPO3H2:H2O (n=1, 2, 3) were hydrothermally investigated. Four phases were obtained and their structures determined by single crystal X-ray diffraction. K4(VIVO)2(VIVO(H2O))4{O3PCH2PO3}4.8H2O or MIL-2K is orthorhombic (S.G. P mmn (n° 59)) with lattice parameters a=13.7642(2) Å, b=15.6796(4) Å, c=4.6902(1) Å, V=1012.23(4) Å3, Z=1. Its three-dimensional framework presents some 14-membered tunnels inserting potassium cations and water molecules. K(VVO(H2O))(VIVO)O{O3P(CH2)2PO3} or MIL-3K is triclinic (S.G. P -1 (n° 2)) with lattice parameters a=7.3807(2) Å, b=7.9984(3) Å, c=10.0641(3) Å, α=75.695(1)°, β=69.178(1)°, γ=80.769(1)°, V=536.37(3) Å3, Z=2. MIL-3K exhibits a pillared structure showing inorganic layers covalently linked by the ethyl chains. Its dehydration is studied. The pillared structures of K(VIVO)2(OH){O3P(CH2)3PO3}3H2O or MIL-7K(HT) and K(V2IV/VO3)(H2O){O3P(CH2)3PO3}H2O or MIL-7K(LT) are closely related, differing only by the neighbouring and the oxidation state of one vanadium atom. Both structures are monoclinic (S.G. C 2/c (n° 15)) with lattices parameters a=14.4939(1) Å, b=10.2595(2) Å, c=18.6782(2) Å, β=98.991(1)°, V=2743.32(6) Å3, Z=8 and a=14.6228(1) Å, b=10.2783(2) Å, c=18.2716(3) Å, β=100.272(1)°, V=2702.16(7) Å3, Z=8 for MIL-7K(HT) and MIL-7K(LT), respectively.

Hydrothermal synthesis and crystal structures of two novel hybrid open-frameworks and a two-dimensional network based on tungsten(vi) oxides

Three new tungsten(VI) oxide hybrid materials, [WO3(pyz)0.5] (pyz=pyrazine) 1, [WO3(bpy)0.5] (bpy = 4,4′-bipyridyl) 2 and [W3O10(enH2)] 3, have been hydrothermally synthesized: 1 and 2 exhibit covalent/coordination hybrid framework connectivities while the structure of 3 consists of novel layers comprised of distorted {WO6} octahedra linked through edge- and corner-sharing interactions.

Hybrid open frameworks (MIL- n): synthesis and crystal structure of MIL-17 — a rare-earth dicarboxylate with a relatively open framework, [Pr(H 2O)] 2[O 2C(CH 2) 2CO 2] 3·H 2O

A new rare-earth dicarboxylate [Pr(H 2O)] 2[O 2C(CH 2) 2CO 2] 3·H 2O (MIL-17) was hydrothermally prepared (180°C, 3 days) by reaction of succinic acid with the metal chloride in the ratio 1:1. The crystal structure of the compound has been determined by single-crystal X-ray diffraction. [Pr(H 2O)] 2[O 2C(CH 2) 2CO 2] 3·H 2O crystallizes in the monoclinic space group C2/c (No. 15) with a=20.2586(8) Å, b=7.9489(3) Å, c=13.9716(5) Å, β=121.641(1)° (final agreement factors R 1=0.0282, wR 2=0.0764). The organic–inorganic network is three-dimensional and consists of edge-sharing rare-earth polyhedra LnO 8(H 2O) chains linked together by the carbon chains along two directions as already encountered in [Pr(H 2O)] 2[O 2C(CH 2) 3CO 2] 3·4H 2O. The connection in [Pr(H 2O)] 2[O 2C(CH 2) 2CO 2] 3·H 2O involves the formation of tunnels large enough to incorporate one weakly bonded water molecule.

Hybrid open-frameworks (MIL-n): Syntheses and structures of 2-dimensional gallium methylphosphonates (MIL-23) and 3-dimensional copper vanadium methyldiphosphonate (MIL-24)

The hydrothermal synthesis and the structure determination from powder or single crystals X-ray diffraction of 3 new metallophosphonates are presented. Crystal data: Ga(OH) 0.28 F 0.72 PO 3 (CH 3 ): P 2 1 / c (n∘ 14), a = 7.7912(7) Å, b = 7.2310(6) Å, c = 9.3114(8) Å, β = 106.873(2) °, V = 502.00(8) Å 3 , Z = 4, R 1 ( F ) = 0.0409, wR 2 ( F 2 ) = 0.0933 for 1 266 reflections I > 2 σ ( I ) with 77 parameters. Ga 3 (OH) 3 F 3 (MePO 3 ) 2 H 2 N(CH 2 ) 3 NH 3 : P -3 (No. 147), a = b = 7.2514(2) Å, c = 7.9413(2) Å, V = 361.6(3) Å 3 , Z = 6, R F = 7.95, R Bragg = 7.18, R wp = 17.3, R p = 12.0. (V IV O(H 2 O))(Cu II (H 2 O))O 3 P-CH 2 -PO 3 : P 2 1 2 1 2 1 (No. 19), a = 6.3884(3) Å, b = 10.7284(4) Å, c = 11.2762(5) Å, V = 772.84(6) Å 3 , Z = 4, R 1 (F) = 0.0395, wR 2 ( F 2 ) = 0.0861 for 2 012 reflections I > 2 σ ( I ) and 128 parameters. Cette publication décrit la synthèse et la structure cristalline de 3 nouveaux metallophosphonates. Les gallophosphonates 1 (Ga(OH) 0.28 F 0.72 PO 3 (CH 3 )) et 2 (Ga 3 (OH) 3 F 3 (MePO 3 ) 2 H 2 N(CH 2 ) 3 NH 3 ) sont bidimensionnels. Dans la structure de 1 , les couches sont formées de chaînes trans d'octaèdres de gallium à sommets communs, reliées entre elles par les groupements phosphonates. La structure de 2 , résolue ab initio à partir d'un diagramme rayons X de poudre, présente une topologie voisine de celle du minéral alunite, avec des couches d'octaèdres de type bronze hexagonal de tungstène capées par le groupement PO 3 du méthylphosphonate. L'amine se situe dans les tunnels hexagonaux de chaque couche. La structure tridimensionnelle de 3 ((V IV O(H 2 O))(Cu II (H 2 O))O 3 P-CH 2 -PO 3 ) peut être décrite par l'empilement de couches d'octaèdres du vanadium (IV) liés entre eux par les groupements diphosphonates. Ces couches sont connectées par des chaînes d'octaèdres CuO 5 (H 2 O) à arêtes communes, qui assurent le caractère tridimensionnel du composé.

Hybrid open frameworks (MIL-n). Part 5 Synthesis and crystal structure of MIL-9: a new three-dimensional ferrimagnetic cobalt(II) carboxylate with a two-dimensional array of edge-sharing Co octahedra with 12-membered rings

Download options Please wait... Article information DOI https://doi.org/10.1039/A802714E Article type Paper Download Citation J. Mater. Chem., 1998,8, 2743-2747 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Hybrid open frameworks (MIL-n). Part 5 Synthesis and crystal structure of MIL-9: a new three-dimensional ferrimagnetic cobalt(II) carboxylate with a two-dimensional array of edge-sharing Co octahedra with 12-membered rings C. Livage, C. Egger, M. Nogues and G. Férey, J. Mater. Chem., 1998, 8, 2743 DOI: 10.1039/A802714E To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author Carine Livage Chrystelle Egger Marc Nogues Gérard Férey

Hybrid open frameworks (MIL-n). Part 3 Crystal structures of the HT and LT forms of MIL-7: a new vanadium propylenediphosphonate with an open-framework. Influence of the synthesis temperature on the oxidation state of vanadium within the same structural type

The hydrothermal synthesis and structure determinations of two vanadium propylenediphosphonate compounds are presented. MIL-7, formulated as [(VO) 2 (OH)(H 2 O){O 3 P(CH 2 ) 3 PO 3 }](H 2 O) 2 (NH 4 ), is synthesized at 200°C. Its structure is monoclinic [space group C2/c (no. 15)] with lattice parameters a=14.2928(2) A, b=10.2440(2) A,c=18.9901(1) A, β=96.658(1)°, V=2761.69(7) A 3 , Z=8. The three-dimensional framework is built up from inorganic V IV -P-O layers strongly related by the alkyl chains. Upon heating hydrothermally the same initial mixture but at 170°C one obtains a different phase, formulated as [V 2 O 3 (H 2 O){O 3 P(CH 2 ) 3 PO 3 }](H 2 O) 2 (NH 4 ), the structure of which is closely related to MIL-7. Its symmetry is monoclinic [space group C2/c (no. 15)] with lattice parameters a=14.8998(8) A, b=10.2903(6) A, c=18.515(1)A,β=101.079(1)°, V=2785.9(3) A 3 , Z=8. The topology of the inorganic layers is almost identical, but presents a mixed valence V IV -V V state in a 1:1 ratio.

Hybrid open frameworks (MIL-n). Part 6 Hydrothermal synthesis and X-ray powder ab initio structure determination of MIL-11, a series of lanthanide organodiphosphonates with three-dimensional networks, LnIIIH[O3P(CH2)nPO3] (n=1-3)

F. Serpaggi and G. Férey, J. Mater. Chem., 1998, 8, 2749 DOI: 10.1039/A802715C

Hybrid open frameworks (MIL-n). Part 4 Synthesis and crystal structure of MIL-8, a series of lanthanide glutarates with an open framework, [Ln(H2O)]2[O2C(CH2)3CO2]3·4H2O

The first series of rare-earth carboxylates with an open framework has been prepared hydrothermally (180°C, 3 days) by the action of glutaric acid on the metal chlorides in the presence of base. The crystal structure of the neodymium compound [Nd III (H 2 O)] 2 [O 2 C(CH 2 ) 3 CO 2 ] 3 ·4H 2 O has been determined by single-crystal X-ray diffraction. The composite material crystallizes in the monoclinic space group C2/c (no. 15) with a=8.1174(1) A, b=15.1841(3) A, c=19.8803(3) A, β=93.762(1)° (final agreement factors R 1 =0.0279, wR 2 =0.0693). The organic-inorganic network is three-dimensional and consists of chains of edge-sharing rare-earth polyedra NdO 8 (H 2 O) along the [100] direction, linked together by the carbon chains along two directions. The connection involves the formation of channels parallel to the rare-earth chains in which weakly bonded water molecules are incorporated. The analogous compounds were obtained with Pr, Sm, Eu, Gd, Dy, Ho and Y.