Bottom up Synthesis That Does Not Start at the Bottom:  Quadruple Covalent Cross-Linking of Nanoscale Faceted Polyhedra

Perry, John J.; Kravtsov, Victor Ch.; McManus, Gregory J.; Zaworotko, Michael J.

doi:10.1021/ja0734952

Cited by 200 publications

(93 citation statements)

References 24 publications

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“…To further evaluate the interaction between the adsorbed CO 2 molecules and the host framework, isosteric heats (Q st ) of CO 2 adsorption were calculated based on the adsorption data collected at 273 K and 298 K by using the Clapeyron method as shown in Figure 4 b. [14] The Q st values at zero loading for 1 and 2 are À51.79 kJ mol À1 and À71.13 kJ mol À1 respectively. The enthalpy value of 2 is higher than that of the previously reported, well-known MIL-100 (63 kJ mol…”

mentioning

confidence: 99%

Tuning CO₂ Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

Parshamoni

Sanda

Jena

et al. 2014

Chemistry An Asian Journal

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The synthesis and characterization of two isoreticular metal-organic frameworks (MOFs), {[Cd(bdc)(4-bpmh)]}n⋅2 n(H2O) (1) and {[Cd(2-NH2bdc)(4-bpmh)]}n⋅2 n(H2O) (2) [bdc = benzene dicarboxylic acid; 2-NH2bdc = 2-amino benzene dicarboxylic acid; 4-bpmh = N,N-bis-pyridin-4-ylmethylene-hydrazine], are reported. Both compounds possess similar two-fold interpenetrated 3D frameworks bridged by dicarboxylates and a 4-bpmh linker. The 2D Cd-dicarboxylate layers are extended along the a-axis to form distorted square grids which are further pillared by 4-bpmh linkers to result in a 3D pillared-bilayer interpenetrated framework. Gas adsorption studies demonstrate that the amino-functionalized MOF 2 shows high selectivity for CO2 (8.4 wt % 273 K and 7.0 wt % 298 K) over CH4 , and the uptake amounts are almost double that of non-functional MOF 1. Iodine (I2 ) adsorption studies reveal that amino-functionalized MOF 2 exhibits a faster I2 adsorption rate and controlled delivery of I2 over the non-functionalized homolog 1.

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confidence: 99%

Tuning CO₂ Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

Parshamoni

Sanda

Jena

et al. 2014

Chemistry An Asian Journal

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“…Therefore, a mixture of Zn 2+ , 5-methylisophthalic acid (H 2 mip), and 1,4-diazabicyclo-[2.2.2]octane (dabco) was allowed to react under solvothermal conditions in DMF. 8 The X-ray single-crystal analysis of the product revealed a non-interpenetrating 3D framework based on Zn 2 (O 2 C) 4 paddlewheel units. 9 The formula deduced from the X-ray structure is [Zn 4 (mip) 4 (dabco)(OH 2 ) 2 ] (1).…”

mentioning

confidence: 99%

“…8 The X-ray single-crystal analysis of the product revealed a non-interpenetrating 3D framework based on Zn 2 (O 2 C) 4 paddlewheel units. 9 The formula deduced from the X-ray structure is [Zn 4 (mip) 4 (dabco)(OH 2 ) 2 ] (1).…”

mentioning

confidence: 99%

Low-Level Self-Assembly of Open Framework Based on Three Different Polyhedra: Metal-Organic Analogue of Face-Centered Cubic Dodecaboride

Chun

2007

J. Am. Chem. Soc.

130

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Coordination polymers or metal-organic frameworks (MOFs) with sustainable void structures enjoy the status as a new class of porous materials with high prospects for practical applications. 1 The network solids have inspired researchers due to the facile synthesis, high crystallinity, and predictable network topologies which collectively are keys for the design of functional materials. 2 One of the topical issues in this area is a new type of MOFs with cage-like polyhedral building units. 3 Metal-organic polyhedral networks are different from typical MOFs having open-channeltype pores in that individual cages carrying large voids are interconnected through relatively small windows. These features could be potentially useful in the storage of small molecules because adsorbed guests may remain kinetically trapped inside the cages.The rational synthesis of such polyhedron-based MOFs is challenging because information on the connectivity around secondary building units (SBUs) does not guarantee the successful prediction of the resulting polyhedra which in turn would form a three-dimensional (3D) net. In light of the new challenges, guidelines have been proposed by several groups. For example, Zaworotko recently reported covalently cross-linked "nanoballs" synthesized using extended organic ligands, 4 and Férey and coworkers used a combination of computational design and targeted synthesis to obtain highly porous MOFs with polyhedral building units. 5 Most of the other examples known in literature are based on synthetic ligands with a rigid and extended backbone. 6 This communication shows that there may be an easier way to reach the same goal. The idea is based on the low-level selfassembly starting from metal ions and simple, unmodified ligands whose coordination modes are well-known. A polyhedron-based porous framework with a high symmetry and a unique topology is thus obtained and presented here.The synthetic efforts have been guided by previous knowledge that dinuclear paddlewheels linked by isophthalate form various 2D nets with calixarene-like triangular or square motifs. 7 When additional linkages are added to such 4-connected nets by placing bridging ligands at the solvent sites of the paddlewheel SBUs, the resulting nets would have topologies somewhat different from typical MOFs with simple channel-type pores. Therefore, a mixture of Zn 2+ , 5-methylisophthalic acid (H 2 mip), and 1,4-diazabicyclo-[2.2.2]octane (dabco) was allowed to react under solvothermal conditions in DMF. 8 The X-ray single-crystal analysis of the product revealed a non-interpenetrating 3D framework based on Zn 2 (O 2 C) 4 paddlewheel units. 9 The formula deduced from the X-ray structure is [Zn 4 (mip) 4 (dabco)(OH 2 ) 2 ] (1).In general, there are two solvent sites in a paddlewheel; however, only one of them is occupied by a bridging dabco ligand in the dinuclear SBU in 1, and another site is coordinated by a water molecule (Figure 1a).Therefore, the paddlewheels in 1 act as 5-connecting nodes with approximately a square pyramid...

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“…In 2007, it was first realized that these polyhedra could be linked due to their octahedral symmetry (O h ) into quadruple cross-linked pcu nets by using a flexible tetracarboxylate based on the mBDC motif [68]. The linker 1,3-bis(5-methoxy-1,3-benzene dicarboxylic acid)benzene (H 4 BMBDB) provides this flexibility, and together with Cu(NO 3 ) 2 in a mixture of dimethyl sulfoxide (DMSO) and dichlorobenzene afforded the predicted MOF.…”

Section: Twelve or Twenty-four Points Of Extension: Metal-organic Polmentioning

confidence: 99%

Reticular Chemistry of Metal-Organic Frameworks Composed of Copper and Zinc Metal Oxide Secondary Building Units as Nodes

Schoedel

Yaghi

2016

The Chemistry of Metal-Organic Frameworks: Synthesis, Characterization, and Applications

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Metal-organic frameworks (MOFs) have attracted enormous scientific interest over the past two decades due to their high crystallinity, exceptional porosity, high modularity, and diverse functionality [1]. The opportunity to achieve functional materials by design with promising properties, unattainable for solid-state materials in general, distinguishes MOFs from any other class of materials, in particular, traditional porous materials, for example, zeolites [2], mesoporous silica [3], and porous carbon [4]. Concepts such as the node and spacer principle [5] are based on simple geometrical analysis, which is facilitated by direct joining of polyhedral or polygonal nodes and linkers to translate their geometry into nets with predictable topology and structure. The obtained crystalline materials represent well-defined structures that allow for studying the design, synthesis, and properties of materials by means of single-crystal X-ray diffraction. Herein, we introduce the concept of secondary building units (SBUs) [1a] as a critical design element for the synthesis of rigid, permanently porous MOFs. Furthermore, the cluster chemistry of copper and zinc is highlighted due to the depth and diversity of their SBU geometries, which allow them to be used in linking with organic units (reticular chemistry) [6]. These will be introduced and exemplified by prominent MOF structures, demonstrating net topologies that have produced numerous functional and expanded frameworks. Secondary Building Units (SBUs): The Design Principles of MOFsIn contrast to molecular building blocks in general [7], which also include single metal nodes, SBUs are defined as an aggregate of metal ions stitched together by multidentate functional groups, such as carboxylates, into clusters (Figure 3.1) [1a]. The SBU term was coined for MOFs as an analogy to SBUs in zeolite chemistry, which are finite or infinite component units that facilitate the structural diversity The Chemistry of Metal-Organic Frameworks: Synthesis, Characterization, and Applications, First Edition. Edited by Stefan Kaskel.

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Bottom up Synthesis That Does Not Start at the Bottom: Quadruple Covalent Cross-Linking of Nanoscale Faceted Polyhedra

Cited by 200 publications

References 24 publications

Tuning CO₂ Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

Tuning CO₂ Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

Low-Level Self-Assembly of Open Framework Based on Three Different Polyhedra: Metal-Organic Analogue of Face-Centered Cubic Dodecaboride

Reticular Chemistry of Metal-Organic Frameworks Composed of Copper and Zinc Metal Oxide Secondary Building Units as Nodes

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Bottom up Synthesis That Does Not Start at the Bottom: Quadruple Covalent Cross-Linking of Nanoscale Faceted Polyhedra

Cited by 200 publications

References 24 publications

Tuning CO2 Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

Tuning CO2 Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

Low-Level Self-Assembly of Open Framework Based on Three Different Polyhedra: Metal-Organic Analogue of Face-Centered Cubic Dodecaboride

Reticular Chemistry of Metal-Organic Frameworks Composed of Copper and Zinc Metal Oxide Secondary Building Units as Nodes

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Tuning CO₂ Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

Tuning CO₂ Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization