Synthesis, X‐ray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on Paddle‐Wheel Motifs: Implications for Hydrogen Storage in Porous Materials

Chun, Hyungphil; Dybtsev, Danil N.; Kim, Hyunuk; Kim, Kimoon

doi:10.1002/chem.200401201

Cited by 832 publications

(543 citation statements)

References 39 publications

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“…NaNO 3 , KNO 3 , NH 4 NO 3 ) led to the formation of the porous 64 and ZIFs 69a using ILAG: (a) the synthesis of pillared MOFs directed by catalytic amounts of nitrate or sulfate ions; (b) the synthesis of ZIFs directed by ionic additives and (c) the stepwise mechanism of ZIF formation leading from a highly porous framework (zeolite RHO topology). framework based on square-grid zinc terephthalate sheets reported by Kim's group, 65 sulfate ion additives led to the formation of supramolecular isomer 66 of this pillared MOF based on hexagonal Kagome topology zinc terephthalate sheets (Figure 8a). 67 These unexpected structure-directing effects were tentatively explained by the inclusion of salts in the MOF porous structure suggested by solid-state NMR and Fouriertransform infrared (FTIR) spectroscopy.…”

Section: Porous Metal-organic Frameworkmentioning

confidence: 83%

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

Friščić¹,

Halász²,

Štrukil³

et al. 2012

Croat. Chem. Acta

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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)

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Section: Porous Metal-organic Frameworkmentioning

confidence: 83%

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

Friščić¹,

Halász²,

Štrukil³

et al. 2012

Croat. Chem. Acta

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“…30 Replacing terephthalic acid by tetramethylterephthalic acid, a non-interpenetrating, porous compound is obtained. 30 Present results show a similar trend. The combination of naphthalenedicarboxylic acid and 4,4¢-bipyridine leads to a threefold interpenetrated structure.…”

Section: Resultsmentioning

confidence: 99%

“…Depending on the size of the dicarboxylic acid it should be possible to fine tune the pore size of the MOF in order to allow the incorporation of the azo-functionalized 4,4¢-bipyridine linker molecule. 30 Here we present the synthesis of the switchable azo-linker molecule 3-azo-phenyl-4,4¢-bipyridine (1), its use in the synthesis of the new porous MOF [Zn 2 (NDC) 2 (1)] named CAU-5 (CAU = Christian-Albrechts-University) and the switching properties of both.…”

Section: Introductionmentioning

confidence: 99%

The first porous MOF with photoswitchable linker molecules

Modrow¹,

Zargarani²,

Herges³

et al. 2011

Dalton Trans.

177

163

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We synthesized a porous twofold interpenetrated MOF [Zn 2 (NDC) 2 (1)] (coined CAU-5) using 3-azo-phenyl-4,4¢-bipyridine (1), 2,6-naphthalenedicarboxylic acid, and Zn(NO 3 ) 2 ·6H 2 O. The azo-functionality protrudes into the pores, and can be switched, by irradiation with UV light (365 nm), from the thermodynamically stable trans-isomer to the cis-isomer. Back-switching was achieved thermally and with an irradiation wavelength of l max = 440 nm.

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“…Here we show that the microwave-assisted coordination modulation controls the crystal size and morphology of the zinc framework that intrinsically grows as submillimeter-sized crystals, [Zn 2 (ndc) 2 (dabco)] n (1: Figures 1a and 1b), 26 wherein the dicarboxylate ndc ligands link the dizinc clusters to form two-dimensional square lattices which are further connected via Nanocrystals of 1 were successfully synthesized when using lauric acid as the modulator; a solution of 1,4-naphthalenedicarboxylic acid (H 2 ndc, 0.06 M) and dabco (0.03 M) in dimethylformamide (DMF) was added to a mixture of zinc acetate (0.06 M) and lauric acid (0.3 M) in DMF at room temperature, and the mixture was immediately heated by microwave irradiation at 373 K for 15 min. The field emission scanning electron microscopy (FE-SEM) image of the obtained materials showed the formation of nanosized rod-shape crystals (Figure 1d), which were much smaller than the powder crystals obtained from the conventional solvothermal method (Figure 1c).…”

mentioning

confidence: 87%

“…2225 This is because the coordination modulation tends to decelerate the nucleation kinetics and helps to grow crystals larger. Therefore, the framework system with slow nucleation kinetics, which grows as a large single crystal, is not suitable.Here we show that the microwave-assisted coordination modulation controls the crystal size and morphology of the zinc framework that intrinsically grows as submillimeter-sized crystals, [Zn 2 (ndc) 2 (dabco)] n (1: Figures 1a and 1b), 26 wherein the dicarboxylate ndc ligands link the dizinc clusters to form two-dimensional square lattices which are further connected via Figure 1. Crystal structure of [Zn 2 (ndc) 2 (dabco)] n and its appearance as nanocrystals.…”

mentioning

confidence: 93%

Formation of Nanocrystals of a Zinc Pillared-layer Porous Coordination Polymer Using Microwave-assisted Coordination Modulation

et al. 2012

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Nanocrystals of three-dimensional pillared-layer type porous coordination polymers, [Zn 2 (ndc) 2 (dabco)] n , were fabricated by microwave-assisted coordination modulation, and its morphology was controlled by changing the modulator concentration. Adsorption measurement supported that the crystallinity and intrinsic porosity were maintained even for nanosized crystals, comparable to the corresponding micrometer-sized bulk powder crystals.Porous coordination polymers (PCPs) or metalorganic frameworks (MOFs) assembled from organic ligands and inorganic joints have been widely investigated due to their potential application in gas storage, adsorptive separation, catalysis, and molecular sensing. 16 Such properties have been traditionally improved by designing functional organic ligands or inorganic clusters and/or by controlling the overall framework topology. Besides these molecular level functionalizations, methodologies to miniaturize the crystal size of PCPs to mesoscale and nanoscale regimes have been recently developed. 79 Thanks to the enhancement of crystal surface contribution or the shortened total diffusion path of resulting nanosized PCP crystals, the crystal downsizing can be recognized as a novel strategy to tune the porous properties. 79 In addition, the fabrication of PCP nanocrystals gives a further opportunity for applications in electronics and biomedicine. 1013 The key to control crystal sizes of PCPs is to regulate the nucleation kinetics in the crystallization process; rapid nucleation gives small crystals and slow kinetics gives large crystals. 14 The simplest method to produce PCP nanocrystals is to use microwave heating, which induces a rapid nucleation, however, simultaneously results in the production of poor crystalline materials, which significantly decrease the porosity. 15,16 On the other hand, the other approach known as microemulsion requires undesired surfactants that might change the porosity of PCPs. 17,18As an alternative method, we recently proposed a novel fabrication protocol, so-called coordination modulation, by changing the coordination equilibrium at the crystal interfaces during the crystallization process, through competitive interactions originating from an additive (modulator) with the same chemical functionality as linker ligands.19 This rather coordination chemistry approach allows us to control both crystallization kinetics and thermodynamics by simply altering the concentration of modulators, which affords the control of crystal size and morphology in nano and meso scales, and to synthesize highly crystalline materials. 20,21 However, the application of this method is, to date, limited to a framework system that intrinsically has a rather fast nucleation process. 2225 This is because the coordination modulation tends to decelerate the nucleation kinetics and helps to grow crystals larger. Therefore, the framework system with slow nucleation kinetics, which grows as a large single crystal, is not suitable.Here we show that the microwave-assisted coordination ...

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Synthesis, X‐ray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on Paddle‐Wheel Motifs: Implications for Hydrogen Storage in Porous Materials

Cited by 832 publications

References 39 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

The first porous MOF with photoswitchable linker molecules

Formation of Nanocrystals of a Zinc Pillared-layer Porous Coordination Polymer Using Microwave-assisted Coordination Modulation

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