Cu<sub>2</sub>(ATC)·6H<sub>2</sub>O:  Design of Open Metal Sites in Porous Metal−Organic Crystals (ATC:  1,3,5,7-Adamantane Tetracarboxylate)

Chen, Banglin; Eddaoudi, Mohamed; Reineke, Theresa M.; Kampf, Jeffrey W.; O’Keeffe, Michael; Yaghi, Omar M.

doi:10.1021/ja003159k

Cited by 479 publications

(273 citation statements)

References 22 publications

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“…tetrafunctionalized rigid tetrahedral platforms, which are in general less investigated compared to their planar counterparts. Once researched actively, with notable results using tetrahedral carboxylate, 10 phosphonate, 11 and sulfonate ligands, 12,13 this direction of research temporarily declined, seemingly due to the perception that tetrahedral platforms yield too dense or interpenetrated structures. Recently there have been signs of revival of the area, partly due to recognition of the fact that the use of massive coordination-bonded clusters as secondary building units (SBU) of high connectedness could be efficient.…”

Section: Introductionmentioning

confidence: 99%

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

et al. 2014

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·62 ·8}, gis or gismondine underlying net, where the role of the tetrahedral nodes is served by the coordination bonded clusters and the adamantane moiety. 3 (P2 1 /n) has a porous structure composed of coordination bonded layers with a (4·8 2 ) fes topology joined via trans-{Zn- The high number of donor functions endows the tetrazolate function with a capability to sustain unusually high number of coordination bonded arrangements ( patterns) 7 compared to other azolates. In the case of simple rigid ligands it is a prerequisite for assembly of a highly symmetric framework, with a † Dedicated to Prof. Marius Andruh on the occasion of his 60th birthday. View Article OnlineView Journal | View Issue significant probability of isomerism. Indeed, the linear 1,4-benzeneditetrazole (H 2 BDT) 8 and flat triangular 1,3,5-benzene- hedral' tetrazolates and involving chloride anions as coligands, serve as an interesting example of variability of coordination-bonded cluster geometry and size due to involvement of short halido bridges. 16,20 It was conjectured that mixed tetrazolato/halido coordination polymers constitute an interesting compound class with 'scalable' multinuclear clusters, 20 which are interesting either as robust SBUs or possibly as functional magnetic units. In this contribution we probed the practically unexplored 1,3,5,7-tetrakis(tetrazol-5yl)adamantane ligand (H 4 L) as a building block for coordination polymers using conditions favoring formation of tetrazolato/halido clusters (Scheme 1). This ligand in anionic form has one of the highest density of donor sites achievable for a 'tetrahedral' ligand, which is a prerequisite for rich coordination and structural chemistry of derived coordination-bonded frameworks. Results and discussion The ligandUniversal rigid molecular platforms with tetrahedral symmetry are typically limited to tetraphenylmethane (including 9,9′-spirobifluorene) and adamantane, as well as their phenyl augmented and heteroatom-substituted analogues.14 Adamantane is the smallest tetrahedral platform next only to quaternary carbon, while the latter has inherent steric limitations. Adamantane is widely used for the synthesis of organic polymers (recently with an emphasis on porous organic polymers and covalent organic frameworks), 22 dendrimers, 23 and molecular entities for supramolecular synthesis 24 and nanotechnology. 25Compared to tetraphenylmethane, whose modification is standard and facile, the chemistry of adamantanes is peculiar, at times cumbersome, but offering synthetic opportunities as well. For example adamantane could be selectively brominated in bridgehead positions to afford mono-to tetra-substituted adamantanes in high yields. 26 However, 1,3,5,7-tetrabromoadamantane is the most chemically inert entity in the row and the substitution of halogens via the S N1 mechanism demands harsh conditions. It was not only until the recent paper of Lee et al.,27 in which photochemical cyanodebromination of 1,3,5,7-tetrabromoadamantane was described that a facile route to various tetra...

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Section: Introductionmentioning

confidence: 99%

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

et al. 2014

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“…Remarkably, 87% of the captured CO 2 can be liberated at room temperature, and the remaining amount can be completely removed by mild heating (80°C). Based on this favorable performance, we assert that MOFs represent a competitive class of materials for efficient CO 2 capture, and that Mg-MOF-74 strikes the right balance between high capacity and heat of adsorption, notwithstanding the great opportunities available for functionalizing such MOFs for even further improved performance.In previous work, it has been shown that coordinatively unsaturated (open) metal sites in MOFs can be prepared by removal of coordinated solvent molecules (7,8). Whereas f lexible molecular or polymeric structures rearrange or aggregate to occlude such reactive sites, the rigidity of MOFs ensures that open metal sites remain accessible to incoming guests.…”

mentioning

confidence: 99%

“…In previous work, it has been shown that coordinatively unsaturated (open) metal sites in MOFs can be prepared by removal of coordinated solvent molecules (7,8). Whereas f lexible molecular or polymeric structures rearrange or aggregate to occlude such reactive sites, the rigidity of MOFs ensures that open metal sites remain accessible to incoming guests.…”

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confidence: 99%

Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites

Britt

Furukawa

Wang

et al. 2009

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

1,049

730

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Selective capture of CO2, which is essential for natural gas purification and CO 2 sequestration, has been reported in zeolites, porous membranes, and amine solutions. However, all such systems require substantial energy input for release of captured CO2, leading to low energy efficiency and high cost. A new class of materials named metal-organic frameworks (MOFs) has also been demonstrated to take up voluminous amounts of CO 2. However, these studies have been largely limited to equilibrium uptake measurements, which are a poor predictor of separation ability, rather than the more industrially relevant kinetic (dynamic) capacity. Here carbon dioxide capture ͉ dynamic adsorption ͉ reticular chemistry S elective removal of CO 2 from gaseous mixtures is of paramount importance for the purification of fuel gases such as methane and acetylene and because of the imminent problem of anthropogenic CO 2 emissions. Effective systems for CO 2 removal must combine high selectivity and capacity with minimal energetic input to liberate the captured CO 2 . Materials presently used are amine solutions, zeolites, and porous membranes, but all fall short in one or more of these categories (1). To date, metal-organic frameworks (MOFs) have been shown to exhibit exceptional CO 2 storage capacity under equilibrium conditions where pure CO 2 is introduced into the pores (2-6). However, their capacities are dramatically reduced when exposed to mixtures of gases under dynamic conditions, as would be the case in power plant f lue gas and methane mining applications. A useful measure of dynamic separation capacity is obtained by exposing the material to mixed gas streams and detecting the appearance or ''breakthrough'' of CO 2 from the material. Here, we report that a MOF replete with open magnesium sites, Mg-MOF-74 [Mg 2 (DOT); DOT: 2,5-dioxidoterephthalate], has excellent selectivity, facile regeneration, and among the highest dynamic capacities reported for CO 2 in porous materials. Specifically, when Mg-MOF-74 is subjected to a gas stream containing 20% CO 2 in CH 4 , a percentage in the range relevant to industrial separations, it captures only CO 2 and not CH 4 . The pores retain 89 g of CO 2 per kilogram of material before breakthrough, a value higher than any other achieved in MOFs, and that rivals the highest capacities in zeolites. Remarkably, 87% of the captured CO 2 can be liberated at room temperature, and the remaining amount can be completely removed by mild heating (80°C). Based on this favorable performance, we assert that MOFs represent a competitive class of materials for efficient CO 2 capture, and that Mg-MOF-74 strikes the right balance between high capacity and heat of adsorption, notwithstanding the great opportunities available for functionalizing such MOFs for even further improved performance.In previous work, it has been shown that coordinatively unsaturated (open) metal sites in MOFs can be prepared by removal of coordinated solvent molecules (7,8). Whereas f lexible molecular or polymeric structures rearran...

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“…The synthesis of metal-organic hybrid materials based on Cu(II) hasbeenanactivefield of research over thepast decades due to theinterestininvestigatingtheir structureand theroleofcopper centers in several catalytic activities, to understand the magnetostructural correlations arisingfromthe exchange coupling among Cu(II) sitesand to developnew molecular magnets [1][2][3][4]. Several bridging ligands have been used to construct such compounds [5][6][7].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of μ2-oxalato-bis[(acetato)(1,10-phenanthroline-κ2N,N')copper(II)], Cu2(C2H3O2)2(C2O4)(C12H8N2)2

Xiao¹

2012

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialBis(1,5-cyclohexanone) oxal dihydrazone( 0.5m mol) wasd issolved in am ixture of water and ethanol (1:1, 25 mL). Then NaOH (0.01 g, 0.25 mmol) was added and the mixture was stirred for 30 min at room temperature. In the next stage, Cu(Ac) 2 × 2H 2 O (0.5 mmol) and 1,10-phenanthroline (phen, 0.5 mmol) were added. Ther eaction mixture was placed in aP arr-Teflon-lined stainless-steel vessel. It wassealed and heated to 120°C for 17 h, then slowly cooled to room temperature. The resultant solution waskeptat4°C. Blue block-shaped crystals were obtained after two weeks. Experimental detailsAllh ydrogena toms were included in calculated positionsa nd treatedasriding with DiscussionThe synthesis of metal-organic hybrid materials based on Cu(II) hasbeenanactivefield of research over thepast decades due to theinterestininvestigatingtheir structureand theroleofcopper centers in several catalytic activities, to understand the magnetostructural correlations arisingfromthe exchange coupling among Cu(II) sitesand to developnew molecular magnets [1][2][3][4]. Several bridging ligands have been used to construct such compounds [5][6][7]. Among them,polycarboxylate ligands have attracted interest as the organic moiety with avariety of coordination modes and abundant structural motifs [8,9]. The title crystal structure is composed of discrete binuclear units Cu 2 (phen) 2 (CH 3 CO 2 ) 2 (C 2 O 4 ). Each Cu(II)i sc oordinated by three oxygen atoms(O1,O3, O4A) from acetate and oxalate and twon itrogena toms from one phen ligand, forming ad istorted trigonal bipyramid, where N1,O 3a nd O4Aa re locateda tt he equatorial positions while N2 and O1 occupy the axial positions. The bond lengths and angles around the Cu(II) are in the ranges of 1.970(3) -2 .237(3) Åa nd 79.9(1) -1 71.1(1)°, respectively. Cu-O distances are in the range of other Cu(II) m 2 -oxalate complexes [10,11]. The oxalate anion is in m 2 -bridging coordination mode to connect the adjacent Cu1 and Cu1Atoform adimer with aCu×××Cu separation of 5.436 Å, while the phen ligand acts as a typical chelate terminally coordinating the Cu(II) center. The dihedral angle between the planes of Cu1,N 2, C11,C 12,N 1 (mean deviation from plane 0.005 Å) and Cu1,O4A,O3A,Cu1A, O4, O3 (mean deviation from plane 0.067 Å) is 72.9°. Moreover, adjacent dimers are arranged into at wo dimensional network, running parallel to (010), by intermolecular C-H×××Ohydrogen-bonding interactions between phen and carboxyl oxygen atoms.

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Cu₂(ATC)·6H₂O: Design of Open Metal Sites in Porous Metal−Organic Crystals (ATC: 1,3,5,7-Adamantane Tetracarboxylate)

Cited by 479 publications

References 22 publications

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites

Crystal structure of μ2-oxalato-bis[(acetato)(1,10-phenanthroline-κ2N,N')copper(II)], Cu2(C2H3O2)2(C2O4)(C12H8N2)2

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Cu2(ATC)·6H2O: Design of Open Metal Sites in Porous Metal−Organic Crystals (ATC: 1,3,5,7-Adamantane Tetracarboxylate)

Cited by 479 publications

References 22 publications

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl2(M = Mn, Cu, Zn, Cd)

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl2(M = Mn, Cu, Zn, Cd)

Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites

Crystal structure of μ2-oxalato-bis[(acetato)(1,10-phenanthroline-κ2N,N')copper(II)], Cu2(C2H3O2)2(C2O4)(C12H8N2)2

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Cu₂(ATC)·6H₂O: Design of Open Metal Sites in Porous Metal−Organic Crystals (ATC: 1,3,5,7-Adamantane Tetracarboxylate)

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)