Temperature and Concentration Control over Interpenetration in a Metal−Organic Material

Zhang, Jianjun; Wojtas, Łukasz; Larsen, Randy W.; Eddaoudi, Mohamed; Zaworotko, Michael J.

doi:10.1021/ja906911q

Cited by 375 publications

(188 citation statements)

References 26 publications

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“…In order to avoid the self-catenation, several strategies have been demonstrated such as liquid-phase epitaxy, 5 template method in synthetic solution, 6 rational design of organic linkers, 7 or modification of the synthetic condition of PCPs. 8 In contrast to this research direction to obtain the larger pore size, a number of studies have demonstrated that entangled frameworks are not quite so bad as once thought, especially thanks to their unique structural dynamics.…”

Section: ç Introductionmentioning

confidence: 99%

Control over Flexibility of Entangled Porous Coordination Frameworks by Molecular and Mesoscopic Chemistries

2013

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Entangled porous coordination frameworks, wherein two or more distinct frameworks are catenated over an entire crystal, are known to demonstrate unique structural flexibilities in response to the accommodation of molecules in the voids between the frameworks. In this highlight review, we introduce key functions of entangled frameworks based on two principles of their dynamic features: shearing and displacement. We further describe strategies to control the flexibilities; one is a molecular chemistry approach to functionalize frameworks by chemical modification, and the other is a mesoscopic chemistry approach to change the physical form, in particular, the crystal size. Ç IntroductionPorous coordination polymers (PCPs) or metalorganic frameworks (MOFs) with three-dimensional (3D) molecular skeleton constructed from organic struts and inorganic nodes are an intriguing class of porous crystalline materials with potential applications in gas storage, separation, catalysis, and sensing. 1These porous properties can be modulated simply by altering the chemical functionalities on the organic struts. Structural flexibility is one of the most characteristic structural features of PCPs, which differentiate among other porous materials. Here, extended frameworks optimize, while maintaining the crystallinity, their structures in response to the incorporation or removal of molecules in the pores. This phenomenon was first anticipated in 1998 and classified as the third generation of PCPs.2 Recently this type of flexible PCPs is defined as soft porous crystals.3 Such structural dynamics originate from either local flexibilities of molecular components, such as intrinsic ligand flexibility and dynamics of coordination environments around metal ions, or global cooperative framework deformations at the scale of crystal domains.Frameworks with periodic interpenetration, 4 wherein two or more distinct frameworks are entangled over an entire crystal, are a good system into which to induce global structural transformation. Entangled frameworks are often spontaneously formed by the elongation of organic spokes in the framework matrices because frameworks prefer to fill the voids by selfcatenation rather than to maintain the large voids therein. The researchers in the field of PCPs and MOFs have, therefore, tried to suppress catenation because the interpenetration generally decreases the pore size and the surface area. In order to avoid the self-catenation, several strategies have been demonstrated such as liquid-phase epitaxy, 5 template method in synthetic solution, 6 rational design of organic linkers, 7 or modification of the synthetic condition of PCPs.8 In contrast to this research direction to obtain the larger pore size, a number of studies have demonstrated that entangled frameworks are not quite so bad as once thought, especially thanks to their unique structural dynamics. 9Entangled frameworks generally exhibit two types of dynamic structural transformations, shearing and displacement. Structural dynamics of ent...

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Section: ç Introductionmentioning

confidence: 99%

Control over Flexibility of Entangled Porous Coordination Frameworks by Molecular and Mesoscopic Chemistries

2013

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“…Although rapid progress in the construction of MOFs has been made, it is still a considerable challenge to control the final structures, because many factors, such as temperature [9,10], solvent [11,12], metal/ligand ratios [13], pH values [14,15], influence the formation of the final structure. O-donor organic ligands, rigid benzene multicarboxylate ligands have attracted considerable attention due to their various coordination modes (monodentate, bridging, chelating).…”

Section: Discussionmentioning

confidence: 99%

Hydrothermal synthesis and crystal structure of a poly[aqua-(μ₄-4-(carboxylatomethyl)benzoato-κ⁴ O:O′:O′′:O′′′)-(μ₂-1-(4-(1H-imidazol-1-yl)benzyl)-1H-1,2,4-triazole-κ² N:N′) dimanganese(II)], [Mn₂(C₉H₆O₄)₂(C₁₂H₁₁N₅)(H₂O)]

Yin

2017

Zeitschrift Für Kristallographie - New Crystal Structures

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C 30 H 25 N5O 9 Mn 2 , monoclinic, P21/c (no. 14), a = 15.5012 (6) CCDC no.: 1560963The asymmetric unit and additional atoms completing the coordination sphere of the manganese atoms is shown in the figure. Source of materialA mixture of Mn(OAc) 2 · 4H 2 O (24.5 mg, 0.1 mmol), homoterephthalic acid (H 2 htpa, 36.0 mg, 0.2 mmol), 1-(imidazolyl)-4-(1,2,4-triazol-1-ylmethyl)benzene (itmb, 22.5 mg, 0.1 mmol) and H 2 O (7 mL) were placed in a 23 mL Teflon-lined autoclave at 393 K for 4 days, then cooled to room temperature. Colourless block crystals were obtained in ca. 86% yield. Elemental analysis calcd. (%) for C 30 H 25 N5O 9 Mn 2 : C, 50.74; H, 3.59; N, 9.88. Found: C, 50.79; H, 3.55; N, 9.87. Experimental detailsAll hydrogen atoms were modelled at their calculated positions and included in the refinement via the riding model. The U iso of the H-atoms were constrained to 1.2 times Ueq of their bonding carbon atoms and 1.5 times Ueq for the hydrogen atoms at water. DiscussionMetal-organic frameworks (MOFs) are one of the most rapidly developing fields in chemical and material sciences and emerging as an important family of porous materials not only because of their fascinating structures, but also due to their excellent properties in the fields of luminescence, magnetism, gas adsorption and catalysis [4][5][6][7][8]. Although rapid

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“…The role of temperature in controlling the assembly process may be rationalized, as higher temperatures would naturally be expected to afford more thermodynamically stable and denser crystal forms. [11] The solid-state CD spectra of 1-3 made from R and S enantiomers of L are mirror images of each other, thus indicating their enantiomeric nature. Calculations using PLATON indicate that 39.8, 59.0, and 45.2 % of the total volume of 1-3, respectively, are occupied by solvent molecules.…”

Section: Methodsmentioning

confidence: 98%

Bottom‐Up Assembly from a Helicate to Homochiral Micro‐ and Mesoporous Metal–Organic Frameworks

Fang

Dong

et al. 2010

Angewandte Chemie

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Temperature and Concentration Control over Interpenetration in a Metal−Organic Material

Cited by 375 publications

References 26 publications

Control over Flexibility of Entangled Porous Coordination Frameworks by Molecular and Mesoscopic Chemistries

Control over Flexibility of Entangled Porous Coordination Frameworks by Molecular and Mesoscopic Chemistries

Hydrothermal synthesis and crystal structure of a poly[aqua-(μ₄-4-(carboxylatomethyl)benzoato-κ⁴ O:O′:O′′:O′′′)-(μ₂-1-(4-(1H-imidazol-1-yl)benzyl)-1H-1,2,4-triazole-κ² N:N′) dimanganese(II)], [Mn₂(C₉H₆O₄)₂(C₁₂H₁₁N₅)(H₂O)]

Bottom‐Up Assembly from a Helicate to Homochiral Micro‐ and Mesoporous Metal–Organic Frameworks

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Temperature and Concentration Control over Interpenetration in a Metal−Organic Material

Cited by 375 publications

References 26 publications

Control over Flexibility of Entangled Porous Coordination Frameworks by Molecular and Mesoscopic Chemistries

Control over Flexibility of Entangled Porous Coordination Frameworks by Molecular and Mesoscopic Chemistries

Hydrothermal synthesis and crystal structure of a poly[aqua-(μ4-4-(carboxylatomethyl)benzoato-κ4 O:O′:O′′:O′′′)-(μ2-1-(4-(1H-imidazol-1-yl)benzyl)-1H-1,2,4-triazole-κ2 N:N′) dimanganese(II)], [Mn2(C9H6O4)2(C12H11N5)(H2O)]

Bottom‐Up Assembly from a Helicate to Homochiral Micro‐ and Mesoporous Metal–Organic Frameworks

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Hydrothermal synthesis and crystal structure of a poly[aqua-(μ₄-4-(carboxylatomethyl)benzoato-κ⁴ O:O′:O′′:O′′′)-(μ₂-1-(4-(1H-imidazol-1-yl)benzyl)-1H-1,2,4-triazole-κ² N:N′) dimanganese(II)], [Mn₂(C₉H₆O₄)₂(C₁₂H₁₁N₅)(H₂O)]