The Silica‐Like Extended Polymorphism of Cobalt(<scp>II</scp>) Imidazolate Three‐Dimensional Frameworks: X‐ray Single‐Crystal Structures and Magnetic Properties

Tian, Yuan; Cai, Chenxin; Ren, Xiao‐Ming; Duan, Chunying; Xu, Yan; Gao, Song; You, Xiao‐Zeng

doi:10.1002/chem.200304957

Cited by 279 publications

(159 citation statements)

References 48 publications

Supporting

Mentioning

150

Contrasting

Unclassified

Order By: Relevance

“…68 We have expanded the use of ILAG for the synthesis of zeolitic imidazolate frameworks (ZIFs), 69a a family of porous MOFs which exploit a combination of tetrahedral metal ions (e.g. Zn 2+ , Co 2+ ) 70 and azolate anions 71 to obtain porous metal-organic topologies analogous to those of zeolites.…”

Section: Porous Metal-organic Frameworkmentioning

confidence: 99%

Clean and Efficient Synthesis Using Mechanochemistry: Coordination Polymers, Metal-Organic Frameworks and Metallodrugs

Friščić¹,

Halász²,

Štrukil³

et al. 2012

Croat. Chem. Acta

View full text Add to dashboard Cite

Abstract. This review briefly discusses recent advances and future prospects in the mechanochemical synthesis of coordination compounds by ball milling and grinding, and highlights our contributions to the mechanosynthesis of porous metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs), metal-organic pharmaceutical derivatives and metallodrugs using the recently developed mechanochemical methods of liquid-assisted grinding (LAG) and ion-and liquid-assisted grinding (ILAG). The role of mechanochemistry in the development of a solvent-free laboratory, cocrystal synthesis and new materials for luminescence and gas absorption is also highlighted. (doi: 10.5562/cca2014)

show abstract

Section: Porous Metal-organic Frameworkmentioning

confidence: 99%

Clean and Efficient Synthesis Using Mechanochemistry: Coordination Polymers, Metal-Organic Frameworks and Metallodrugs

Friščić¹,

Halász²,

Štrukil³

et al. 2012

Croat. Chem. Acta

View full text Add to dashboard Cite

show abstract

“…We believed that it should be possible under the right conditions to prepare metal IMs adopting open-framework zeolite structures. Indeed, a number of relatively new Fe(II) (5), Co(II) (6,7), Cu(II) (8), and Zn(II) (9) IM compounds have structures that are based on zeolite-like tetrahedral nets. However, these materials are relatively dense (nonporous) and͞or low-symmetry structures.…”

mentioning

confidence: 99%

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

Park

Côté

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

6,443

314

5,102

View full text Add to dashboard Cite

Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area ‫؍‬ 1,810 m 2 ͞g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.catalysis ͉ hydrogen storage ͉ metal-organic frameworks ͉ porosity ͉ zeolites A large segment of the global economy ($350 billion) is based on the use of crystalline microporous zeolites in petrochemical cracking, ion-exchange for water softening and purification, and in the separation of gases (1). Zeolite structures are composed of tetrahedral Si(Al)O 4 units covalently joined by bridging O atoms to produce Ͼ150 different types of framework (2). A long-standing challenge is to incorporate transition metal ions and organic units within their pores and, more desirably, to do so as an integral part of the zeolite framework. This ability would be useful in many catalytic applications because the pores would be lined with a high concentration of ordered transition metal sites whose electronic and steric properties can be tailored by functionalization of the organic links. However, the vision of achieving such a zeolite that combines these features remains largely unrealized. Here, we outline a general synthesis of structures having zeolite framework topologies in which all tetrahedral atoms are transition metals, and all bridging ones are imidazolate (IM) units.Imidazole can lose a proton to form IM, 1. In examining the dense-phases Co(IM) 2 and Zn(IM) 2 , whose structures are based on nets of linked CoN 4 or ZnN 4 tetrahedra (3, 4), we noticed that IM bridges make an M-IM-M angle, 1, close to 145°, which is coincident with the Si-O-Si angle, 2, which is preferred and commonly found in many zeolites (see Scheme 1). We believed that it should be possible under the right conditions to prepare metal IMs adopting open-framework zeolite structures. Indeed, a number of relatively new Fe(II) (5), Co(II) (6, 7), Cu(II) (8), and Zn(II) (9) IM compounds have structures that are based on zeolite-like tetrahedral nets. However, these materials are relatively dense (nonporous) and͞or low-symmetry structures. Only very recently, Zn(II) IMs having symmetrical porous structures analogous to zeolites were reported (10). Two of the aforementioned compounds are included, as zeolitic IM framework (ZIF)-7 and -8, among the library of ZIFs we report here (Fig. 1).** The focus of th...

show abstract

“…elastic properties | metal-organic frameworks | nanohardness | nanoporosity | zeolitic imidazolate frameworks Z eolitic imidazolate frameworks (ZIFs) represent a unique class of metal-organic frameworks (MOFs) in which the network topology and related properties vary greatly while core chemical connectivity is retained (1,2). ZIFs currently attract considerable interest by virtue of their exciting potential for hydrogen storage and carbon dioxide capture (3,4).…”

mentioning

confidence: 99%

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

Tan

Bennett

Cheetham

2010

Proc. Natl. Acad. Sci. U.S.A.

493

451

View full text Add to dashboard Cite

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 structuremechanical property relationships pertaining to hybrid open frameworks that are important for the design and application of new MOF materials.elastic properties | metal-organic frameworks | nanohardness | nanoporosity | zeolitic imidazolate frameworks Z eolitic imidazolate frameworks (ZIFs) represent a unique class of metal-organic frameworks (MOFs) in which the network topology and related properties vary greatly while core chemical connectivity is retained (1, 2). ZIFs currently attract considerable interest by virtue of their exciting potential for hydrogen storage and carbon dioxide capture (3, 4). They adopt porous crystalline structures composed of metal ions and organic linkers, ordered in an analogous fashion to that of silicon and oxygen in zeolites. Specifically, tetrahedral metal centers [typically M ¼ ZnðIIÞ or Co(II)] that are solely coordinated by nitrogen atoms in the 1,3-positions of the imidazolate bridging ligand (Im ¼ C 3 N 2 H − 3 ), subtend an angle of 145°at the M-Im-M center (i.e., analogous to the Si-O-Si angle in silicas and zeolites). Such hybrid architectures can, importantly, give rise to a multitude of extended 3D open frameworks with topologies akin to those found in aluminosilicate zeolites. Over 90 distinct ZIF structures based on 36 of these tetrahedral topologies have been discovered thus far (5). Remarkably, ZIFs combine the classical zeolitic traits of chemical and thermal stability with the rich topological diversity and pore size tunability characteristic of MOFs (6, 7).By and large, research into MOF materials has been motivated by the prospect of discovering new structures with enhanced functional properties for use not only in gas adsorption and separation fields, but also in heterogeneous catalysis and molecular sensing applications (8-11). Indeed, all the aforementioned applications involve subjecting the porous systems to various modes of mechanical stresses and strains, for which their mechanical properties are critical to reach practical implementations. For instance, the open framework needs to exhibit good stiffness, rigidity, and robu...

show abstract

The Silica‐Like Extended Polymorphism of Cobalt(II) Imidazolate Three‐Dimensional Frameworks: X‐ray Single‐Crystal Structures and Magnetic Properties

Cited by 279 publications

References 48 publications

Clean and Efficient Synthesis Using Mechanochemistry: Coordination Polymers, Metal-Organic Frameworks and Metallodrugs

Clean and Efficient Synthesis Using Mechanochemistry: Coordination Polymers, Metal-Organic Frameworks and Metallodrugs

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

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

Contact Info

Product

Resources

About