Extended Polymorphism in Copper(II) Imidazolate Polymers:  A Spectroscopic and XRPD Structural Study

Masciocchi, Norberto; Bruni, Silvia; Cariati, Elena; Cariati, F.; Galli, Simona; Sironi, Angelo

doi:10.1021/ic010384+

Cited by 165 publications

(113 citation statements)

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“…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.…”

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confidence: 99%

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

Park

Côté

et al. 2006

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

6,435

314

5,102

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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...

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mentioning

confidence: 99%

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

Park

Côté

et al. 2006

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

6,435

314

5,102

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“…In the present work, we have extended our studies on the aerobic oxidation of tetralin to a copper-containing MOF, [Cu(im) 2 ] (im = imidazolate, 12 ), which has a chemical composition and crystalline structure related to that of [Cu(2-pymo) 2 ]. Recently, we have successfully used both materials for coupling reactions; viz.…”

Section: Introductionmentioning

confidence: 99%

Selective aerobic oxidation of activated alkanes with MOFs and their use for epoxidation of olefins with oxygen in a tandem reaction

Luz

León

Boronat

et al. 2013

Catal. Sci. Technol.

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“…Particularly,c opper complexes containing heterocycles have been investigatedextensivelytodate [3,4]. On the other hand, it is well known that carboxylate and pyridine groups have good coordination capacities as well as the amide group, af ascinating functional groupw itht wo differentt ypes of hydrogen bonding sites: the -NH moiety which acts as an electron acceptor while the -C=O groupactsasanelectron donor [5][6][7][8].…”

Section: Discussionmentioning

confidence: 99%