Open Metal-organic Frameworks Research Articles

Step-by-Step Route for the Synthesis of Metal−Organic Frameworks

Using a novel layer-by-layer approach we have deposited metal−organic open frameworks (MOFs) based on benzenetricarboxylic acid ligands and Cu(II)-ions on a COOH-terminated organic surface. The deposited layers were characterized using a number of surface analysis techniques. XRD measurements show that the MOFs deposited using this method have the same bulk structure of HKUST-1.

An Illustration of the Limit of the Metal Organic Framework's Isoreticular Principle Using a Semirigid Tritopic Linker Obtained by “Click” Chemistry

A new nitrogen-rich tricarboxylate linker was prepared by “click” chemistry and used for the preparation of a lanthanum-based open metal organic framework. This latter is built of inorganic 1-D rods connected through the tritopic linkers and illustrates one limit of the isoreticular principle, which is related to the partial flexibility of the linkers.

Unprecedented interweaving of single-helical and unequal double-helical chains into chiral metal–organic open frameworks with multiwalled tubular structures

Unprecedented interweaving of single-helical and unequal double-helical chains into chiral metal–organic open frameworks with multiwalled tubular structures

Unprecedented interweaving of single-helical and unequal double-helical chains into chiral metal–organic open frameworks with multiwalled tubular structures

Two novel chiral metal-organic open frameworks with unprecedented multiwalled tubular channels and interweaving of single-helical and unequal double-helical units were reported, which possess novel four-connected 4(2)8(3)10 topology and represent the first examples of functional metal-organic frameworks based on both flexible tripodal and flexible bisdentate ligands.

Recent Advances in the Dynamics of Single Crystal to Single Crystal Transformations in Metal—Organic Open Frameworks

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Construction of Polyoxometalates-Based Coordination Polymers through Direct Incorporation between Polyoxometalates and the Voids in a 2D Network

A series of polyoxometalates (POMs)-based coordination polymers, namely, {[Cu(2,3-Me2pz)(2,5-Me2pz)0.5]4(SiW12O40)(2,5-Me2pz)}n (2,3-Me2pz = 2,3-dimethylpyrazine; 2,5-Me2pz = 2,5-dimethylpyrazine; 1), {[Cu2(4,4'-bipy)4(H2O)4](SiW12O40)(H2O)18}n (4,4'-bipy = 4,4'-bipyridine; 2), {[Cu(2-Mepz)1.5]3(PMo12O40)(H2O)3.5}n (2-Mepz = 2-methylpyrazine; 3), {[Ag(2,3-Me2pz)1.5]4(SiW12O40}n (4), {[Cu(pz)1.5]4(SiW12O40)(H2O)3}n (pz = pyrazine; 5), {[Cu(2,3-Me2pz)1.5]4(SiW12O40)}n (6), {[Cu(4,4'-bipy)1.75]4(SiW12O40)(H2O)2}n (7), and {[Cu2(4,4'-bipy)4(H2O)4](SiW12O40)(4,4'-bipy)2(H2O)4}n (8), were synthesized through direct incorporation between POMs and the voids of the 2D network. Crystal structural analysis reveals that the relationship between the size of the void of the 2D network and that of POMs is of key importance for successful synthesis of POMs-based open metal-organic frameworks. Guest replacement shows that the pore size of the framework constructed through direct incorporation between POMs and the voids of the 2D network is very sensitive to guest molecules.

A Multifunctional Metal–Organic Open Framework with a bcu Topology Constructed from Undecanuclear Clusters

Große Poren dank flexibler Liganden: Ein neuartiges metall-organisches Gerüst aus Cadmiumcarboxylat-Clustern als sekundären Baueinheiten und HCOOH als Brückengruppen wurde hergestellt (siehe Bild). Das poröse Material hat eine seltene innenzentrierte kubische Topologie und weist gute Sorptions- sowie optoelektronische Eigenschaften auf.

A Multifunctional Metal–Organic Open Framework with a bcu Topology Constructed from Undecanuclear Clusters

Flexible ligands afford large pores: A novel metal–organic framework constructed from cadmium carboxylate cluster secondary building units and formic acid bridging molecules is reported (see picture). This highly porous material displays rare body-centered cubic topology, as well as good sorption characteristics and optoelectronic properties.

Construction of Open Metal–Organic Frameworks Based on Predesigned Carboxylate Isomers: From Achiral to Chiral Nets

The four-connected carboxylate ligand N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine (TCPPDA) exists as three stereoisomers: a pair of enantiomers (deltaD2- and lambdaD2-TCPPDA) and a diastereomer (C2h-TCPPDA). TCPPDA was predesigned for the construction of isomeric coordination networks. Reactions of M(NO3)2 (M=Cu, Zn, Co) or Nd(NO)3 with TCPPDA under solvothermal conditions gave rise to five novel porous metal-organic frameworks: [Cu2(D2-tcppda)(H2O)2].2 DMSO.6H2O (1), [Cu2(C2h-tcppda)(H2O)2].2DMSO.6H2O (2), [Co3(D2-Htcppda)2].4DEF.5H2O (3), [Nd2(D2-tcppda)(C2h-tcppda)0.5(DMSO)3]3 DMSO5 H2O (4), and [Zn4O(D2-tcppda)1.5].DMF.H2O (5) (DMSO=dimethyl sulfoxide, DEF=diethylformamide, DMF=dimethylformamide). Complexes 1 and 2 are supramolecular isomers, in which all the ligands adopt pseudotetrahedral (both deltaD2- and lambdaD2-TCPPDA) and rectangular (C2h-TCPPDA) geometries, respectively. Both compounds connect paddlewheel secondary building units (SBUs) to form three-dimensional porous networks possessing PtS and NbO nets, respectively. In 3, all ligands possess pseudotetrahedral (both deltaD2- and lambdaD2-TCPPDA) geometry and link hourglass SBUs to form a three-dimensional porous framework. Compound 4 contains all three stereoisomers (C2-, deltaD2-, and lambdaD2-TCPPDA), thus, has both pseudotetrahedral and rectangular geometries. D2-TCPPDA connects the binuclear neodymium units to generate a two-dimensional layer, further linked by C2h-TCPPDA to create a three-dimensional open framework. In 5, all the ligands possess pseudotetrahedral geometry (D2-TCPPDA), as found in 1 and 3. However, all the TCPPDA ligands in 5 appear as either the deltaD2 or the lambdaD2 form, thus, the whole structure is homochiral. Complex 5 crystallizes in the I4(1)32 space group and the octahedral SBU in 5 is connected by the enantiopure TCPPDA to generate a three-dimensional porous network possessing the corundum Al2O3 net. Complexes 1, 2, and 5 possess permanent porosity, and 4 and 5 exhibit strong luminescence at lambdamax=423 and 424 nm, respectively, upon excitation at 268.5 nm.

Recent Advances in the Dynamics of Single Crystal to Single Crystal Transformations in Metal–Organic Open Frameworks

Single crystal to single crystal transformations have been the subject of growing interest in recent years. In this article, several examples of single crystal to single crystal transformations that occur in metal–organic open frameworks (MOFs) upon guest removal and rebinding, guest exchange, and chemical oxidation are introduced. Depending on the structures of the MOFs, host framework structures can be retained or altered upon guest removal. When host framework structures are altered, significant rearrangements of the molecular components, which involve sponge-like shrinkage/swelling, sliding, swing, bending, and/or rotational motions, occurs throughout the entire crystal to retain the single crystallinity.

A microporous coordination polymer with 1-D channels constructed from a basic reaction system

A ytterbium coordination polymer, {[Yb2(OH)2(atpt)2]·0.5H2O} n , (atpt = 2-aminoterephthalate) was synthesized by using the reaction of YbCl3·6H2O with 2-aminoterephthalic acid under hydrothermal condition and structurally characterized by single-crystal X-ray diffraction method. The Yb(III) complex crystallizes in the monoclinic system P2/c with a = 13.1306(9) A, b = 7.8049(5) A, c = 21.5601(12) A, β = 111.481(3)°, V = 2056.1(2) A3, Z = 4. There are two crystallographically independent Yb3+ ions in the crystal, in which one is seven-coordinate, the other is eight-coordinate, and both of them are in oxygen environments. The ligand atpt adopts two coordination modes, bis(bridging bidentate) and bis(chelating and bridging tridentate). In addition, every hydroxyl group adopts μ3-O mode linking three Yb3+ ions. It is through the linkage of atpt and hydroxyl group that ytterbium ions are linked together to form a 3-D structure with an open metal–organic framework.

Selective Nucleation and Growth of Metal−Organic Open Framework Thin Films on Patterned COOH/CF3-Terminated Self-Assembled Monolayers on Au(111)

Metal-Organic open Framework coordination polymers (MOFs) are a fascinating class of materials. We demonstrate the selective growth of patterned thin films of MOF-5 and the subsequent loading with a palladium organic compound, which acts as a precursor for the deposition of palladium nanoclusters inside the cavities of the MOF-5 material.

Mn(II) Staircase Structures Stitched by Water Clusters to a 3D Metal-Organic Open Framework: X-ray Structural and Magnetic Studies

4-Hydroxypyridine-2,6-dicarboxylic acid (chelidamic acid, cdaH2) reacts with Mn(OAc)2 x 4H2O to form a 1D staircase structure with dimeric Mn(II) units connected by water clusters to form a 3D framework, {[Mn2(cda)2 x 4H2O] x 4H2O}n, 1, in aqueous pyridine at room temperature. The compound crystallizes in the triclinic space group P1 with a = 9.495(3), b =10.733(5), c = 11.065(4) A, alpha = 87.42(5), beta = 74.14(5), gamma = 80.07(2) degrees, U = 1068.5(9) A3, Z = 2, rho(calcd) = 1.915 g cm(-3), T = 100 K, mu = 1.28 mm(-1), R1 = 0.0453 (I > 2sigma(I)), wR2 = 0.1046, GOOF = 1.282. Upon removal of the water molecules by heating, the 3D structure breaks down. Thermogravimetric analysis, infrared, X-ray powder diffraction studies, and X-ray crystallography were performed to characterize this compound. Since the coordination polymer has diaqua-bridged Mn(II) centers, it was subjected to variable-temperature magnetic studies.

Redox‐Active Porous Metal–Organic Framework Producing Silver Nanoparticles from AgI Ions at Room Temperature

However, metal–organic open frameworks areoften not robust, so they collapse when the guest moleculesoccupying the voids are removed, and thus applications arestill very limited compared to those for zeolites.The preparation of monodispersed silver nanoparticleshas attracted great attention because they exhibit a strongsurface plasmon resonance that depends on the particle sizeand shape.

New double-layered open metal–organic frameworks with nanosized channels encapsulated removable 2,5-bis(4-pyridyl)-1,3,4-thiadiazole molecules

Download options Please wait... Article information DOI https://doi.org/10.1039/B417741J Article type Paper Submitted 24 Nov 2004 Accepted 22 Dec 2004 First published 24 Jan 2005 Download Citation CrystEngComm, 2005,7, 96-101 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions New double-layered open metal–organic frameworks with nanosized channels encapsulated removable 2,5-bis(4-pyridyl)-1,3,4-thiadiazole molecules X. Zhang, R. Fang and H. Wu, CrystEngComm, 2005, 7, 96 DOI: 10.1039/B417741J 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. Social activity Tweet Share Search articles by author Xian-Ming Zhang Rui-Qin Fang Hai-Shun Wu

Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework.

A new three-dimensional (3-D) jungle-gym-like open metal-organic framework has been synthesized from a two-dimensional (2-D) layer compound using a heterogeneous pillar insertion reaction. Both the starting 2-D layer and the resulting 3-D open compounds have been characterized using X-ray crystallography.

A New Open Metal-Organic Framework [Zn8(GeO4)(C8H4O4)6]n, Constructed by Heterometallic Cluster Zn8(GeO4) Secondary Building Units

Abstract A new interpenetrating three dimensional open metal–organic framework [Zn8(GeO4)(C8H4O4)6]n, constructed by Zn8(GeO4) secondary building units is reported. It is a rare example of metal–organic frameworks based on the heterometallic cluster secondary building units. Thermogravimetric analysis shows that it is thermally stable up to 320 °C.

QMOF-1 and QMOF-2: three-dimensional metal-organic open frameworks with a quartzlike topology.

Man-made minerals: The synthesis of two α- and β-quartz structures with open metal–organic frameworks (QMOF-1 and QMOF-2) is reported. QMOF-1 is assigned to Zn(ISN)2⋅2 H2O (ISN=isonicotinic acid) with the low symmetry of α-quartz, while QMOF-2 to InH(BDC)2 (BDC=terephthalate) with the high symmetry of β-quartz.

Co5(im)10⋅2 MB]∞: A Metal-Organic Open-Framework with Zeolite-Like Topology This work was funded by the State Key Project of Fundamental Research (No. G200077500) and the Natural Science Foundation of China. We thank Prof. Dr. Ren-Gen Xiong for production of figures. im=imidazole; MB=3-methyl-1-butanol.

Ein hoch robuster metallorganischer Zeotyp wurde durch Expandieren der Zeolithtopologie hergestellt. Das neuartige nanoporöse Material [Co5(im)10⋅2 MB]∞ (siehe Struktur) hat nicht nur eine Zeolith-ähnliche Topologie, sondern weist auch die chemisch funktionalisierbaren Eigenschaften von Zeolithen auf. im=Imidazol; MB=3-Methyl-1-butanol.

A Two-Dimensional Polyrotaxane with Large Cavities and Channels: A Novel Approach to Metal-Organic Open-Frameworks by Using Supramolecular Building Blocks.

A seven-membered molecular necklace composed of six copper ions and six pseudorotaxane units behaves as a secondary building block in the formation of a two-dimensional polyrotaxane network with large voids. This novel metal-organic framework allows size-selective anion exchange as well as the exchange of coordinated ligands. Thus a new synthetic strategy has been identified for modular porous solids which utilizes large, rigid, interlocked supermolecules as primary or secondary building blocks.