Selective Generation of Organic Aggregates Included within Metal−Organic Micropores through Vapor Adsorption

Takamizawa, Satoshi; Saito, T.; Akatsuka, Takamasa; Nakata, Ei-ichi

doi:10.1021/ic048351s

Cited by 74 publications

(88 citation statements)

References 25 publications

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“…Therefore, to elucidate the structure of the adsorbed molecules, we first performed in situ X-ray powder diffraction (XRPD) measurements for CPL-1 accommodating O 2 molecules, and succeeded in determining a 1D ladder molecular array structure of O 2 . Direct observation of guest molecules accommodated in porous materials by Xray and neutron structural analysis is very useful to study guest adsorption phenomena [46][47][48][49][50][51][70][71][72][73][74][75][76][77][78][79][80][81][82]. The overall crystal structure and geometry of the O 2 molecules are represented in Fig.…”

Section: Formation Of Molecular Arrays In Cpl-1mentioning

confidence: 99%

“…Recent studies have explored the rotational motion of the aromatic rings, which very often exist in the structure, showing that they can afford new flexible features in the porous coordination polymers [78,79,81,82,136,139,165].…”

Section: Rotational Motion Of Aromatic Ringsmentioning

confidence: 99%

“…26) [78,79,81,82,166,167]. The component chains found in crystals of 1 adopt a perfectly linear geometry with the chain skeleton bridged by the pyrazine group in the axial direction of the wellknown paddle wheel type of dinuclear rhodium benzoate.…”

Section: Rotational Motion Of Aromatic Ringsmentioning

confidence: 99%

See 2 more Smart Citations

Chemistry of coordination space of porous coordination polymers

Kitagawa

Matsuda

2007

Coordination Chemistry Reviews

907

406

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Section: Formation Of Molecular Arrays In Cpl-1mentioning

confidence: 99%

Section: Rotational Motion Of Aromatic Ringsmentioning

confidence: 99%

See 1 more Smart Citation

Chemistry of coordination space of porous coordination polymers

Kitagawa

Matsuda

2007

Coordination Chemistry Reviews

907

406

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“…14,36,40,41,53,61,67,75,95,97120 Within these structural conversions, we were able to see many instances of (1) coordination bond cleavage and formation, 36,40,121123 (2) hydrogen bond cleavage and formation, 93,124 and (3) changes in the rotation and orientation of organic molecules. 58,60,61,114,117,125,126 These factors arose due to PCPs being inorganic and organic complexes. We performed experiments in trying to change the absorption properties of the guest molecule through controlling dynamic structural conversions using various organic ligand modifications.…”

Section: Porous Coordination Polymer Having Molecular Gatesmentioning

confidence: 99%

Design and Synthesis of Porous Coordination Polymers Showing Unique Guest Adsorption Behaviors

Matsuda

2013

Bulletin of the Chemical Society of Japan

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Gas storage and separation are becoming a high priority area of research due to economic, industrial, and environmental reasons. The last two decades have therefore witnessed dramatic growth in the search for more efficient and adaptable nanoporous materials. In particular, much attention has been focused on porous coordination polymers (PCPs) or metal organic frameworks (MOFs) as new nanoporous materials. Based on the unlimited combination of metal ions and organic ligands, PCPs can provide infinite variety of nanospace in their pores. As molecular adsorption is dependent on the size, shape, and surface nature of nanospace, many unique molecular adsorption or trapping phenomena have been reported in this class of compounds. In this account, I focus on how thoughtful design can lead to the synthesis of porous coordination polymers that demonstrate unprecedented adsorption behavior not found in other porous materials. Examples include selective adsorption of acetylene over carbon dioxide in the CPL series of PCPs, using charge-transfer to induce selective adsorption of nitric oxide and oxygen in TCNQ (7,7,8,8-tetracyano-p-quinodimethane) based PCP and lightinduced on-demand adsorption and structural transformations in CID-based PCPs. The guidelines underpinning such unique, highly selective guest adsorption are discussed.

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“…An estimation by the Clausius-Clapeyron equation gives an adsorption enthalpy of 52.0 kJ mol À1 in 1 (inset in Figure 4 a), which is slightly larger than that of bulk water condensation (44 kJ mol À1 ), thus indicating the moderate hydrating and dehydrating ability of 1 not only by the Coulombic potential for the stabilization of adsorbed polar water molecules but also by reduction of the ionic character of [Co(en) 3 ] 3+ through the encapsulation of organic ligands. The abrupt increase in adsorption of water vapor by 1 indicates a "mass-induced phase transition," [9] which suggests the reversible shrinkage and expansion of 1 through gas adsorption triggered by the formation of specific water aggregation as well as by the increased amount of adsorbed water.…”

mentioning

confidence: 99%

Gas‐Conforming Transformability of an Ionic Single‐Crystal Host Consisting of Discrete Charged Components

2008

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Tris(ethylenediamine)cobalt(III) chloride, [Co III (en) 3 ]Cl 3 (en = ethylenediamine), is one of the most fundamental compounds of coordination chemistry. Although the wellknown ethylenediamine complexes may be regarded as well studied, research that considers their gas-adsorbent ability has not been reported. The racemic hydrated crystal of (AE )-[Co(en) 3 ]Cl 3 (1) includes H 2 O molecules within the onedimensional channels (see Figure 1).[1] Although the "zeolitic" behavior of 1 as a hydrate and dehydrate was reported in 1959,[2] the gas-adsorption ability of dried crystals of 1 was recently euphemistically indicated in 2002 and 2003 by a solidstate NMR spectroscopic study of n-alkanes under saturated vapor as well as of loaded Xe gas at high pressure.[3] Currently, porous materials based on metal complexes are very attractive research targets owing to their designable structure, unusual flexibilities, and projected tunable functions. [4] Dynamic porosity has been given much attention for the function of dynamic guest inclusion, [4][5][6] which can control guest reactivity and stability. [7] In the context of host dimensionality and binding forces for the component skeletons, currently the most actively investigated materials generally consist of polymeric skeletons with the assistance of van der Waals interpolymer interactions. Such structures should be well restricted in their transformability regarding the direction and range of motion by how the 3D architecture is constructed. Thus, an ionic crystal consisting of charged spherical components can be considered to possess extremely unrestricted transformability, which is regulated mostly by the minimization of the ionic-crystal energy under the various gas-adsorbing states. In this case, the Coulombic potential is rather "loose" in terms of binding interaction, which is generated in isotropic radial directions over a long distance proportional to r À1 (r = intermolecular distance), whereas that of van der Waals interactions is proportional to r À6 . Thus, there is a possibility that the ionic crystal can transform its crystal structure to sensitively adapt to the various adsorbedguest properties even by weak physisorption. Because crystal 1 seems to satisfy these requirements for the target-flexible ionic porosity, we focus on the gas adsorbency of ionic crystal 1. The purely van der Waals molecular crystal host is known for the cyclotriphosphazene inclusion compound. [8] Well-formed hydrated single crystals of 1 ([Co III (en) 3 ]Cl 3 ·4 H 2 O) were obtained as hexagonal rods by recrystallization from water. The structure has 1D channels running along the rod axis perpendicular to the hexagonal (001) plane, forming a channel crystal with 1D penetration pores (Figure 2). Single-crystal X-ray diffraction analysis demonstrated the 1D channel structure of 1 including a 1D water chain with the infinite connectivity of a trigonalbipyramidal periodic unit (Figure 3 a). After vacuum drying at 60 8C, single-crystal X-ray diffraction analysis can be perform...

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Selective Generation of Organic Aggregates Included within Metal−Organic Micropores through Vapor Adsorption

Cited by 74 publications

References 25 publications

Chemistry of coordination space of porous coordination polymers

Chemistry of coordination space of porous coordination polymers

Design and Synthesis of Porous Coordination Polymers Showing Unique Guest Adsorption Behaviors

Gas‐Conforming Transformability of an Ionic Single‐Crystal Host Consisting of Discrete Charged Components

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