Azacalix[7]arene Heptamethyl Ether: Preparation, Nanochannel Crystal Structure, and Selective Adsorption of Carbon Dioxide

Tsue, Hirohito; Matsui, Kazuhiro; Ishibashi, Koichi; Takahashi, Hiroki; Tokita, Satoshi; Ono, Kohei; Tamura, Rui

doi:10.1021/jo801543z

Cited by 48 publications

(16 citation statements)

References 51 publications

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“…136 Other examples include Ag + selective calix [4]arene based dipodal hosts, 137 calix[4]azacrowns 138 and azacalix [7]arene heptamethyl ether. 139 In every case an important contribution of CH/p hydrogen bonds has been recognized.…”

Section: Calixarene-derived Hostsmentioning

confidence: 99%

CH/π hydrogen bonds in organic and organometallic chemistry

Nishio¹,

et al. 2009

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Section: Calixarene-derived Hostsmentioning

confidence: 99%

CH/π hydrogen bonds in organic and organometallic chemistry

Nishio¹,

et al. 2009

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“…129 A number of macrocycles align within crystals to give NMCs with 1-D channels, sometimes termed 'supramolecular nanotubes'. These include the family of torus-shaped cucurbit[n]urils (n ¼ 5, 6 and 8), 130,131 for which gas adsorption studies of the crystal of cucurbit [6]uril 11 confirm nanoporosity, 98 a bis-urea macrocycle 12 shown to adsorb CO 2 , 99,100 macrocycles aligned via calcogen-calcogen interactions, 132 a macrocyclic dimer of a tetra-aryl-1,3-dioxolane-4,5-dimethanol (TADDOL) chiral ligand that in its unsolvated form can adsorb ether, 133 azacalixarenes that adsorb CO 2 selectively from air, 134,135 and a number of metal-organic macrocycles formed through coordination chemistry, some of which demonstrate gas adsorption subsequent to removal of included solvent. 76,[136][137][138][139][140][141][142][143] A very recent paper describes a remarkable gallium-based 'molecular wheel' which has been shown to possess nanoporosity by hyperpolarized 129 Xe NMR.…”

Section: Molecular Nanoporous Crystals With 1-d Channelsmentioning

confidence: 99%

Nanoporous molecular crystals

2010

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Nanoporous Molecular Crystals (NMCs) are nanoporous materials composed of discrete molecules between which there are only non-covalent interactions-i.e. they do not possess an extended framework composed of covalent or coordination bonds. They are formed from removing guest molecules from inclusion compounds (ICs) a process that for most ICs usually results in the collapse of the open structure of the crystals but in the case of NMCs the packing of the host molecules is retained and nanoporosity obtained. In recent years a number of NMCs have been confirmed by the technique of gas adsorption and these materials are surveyed in this feature article. In addition, the reasons for stability of these crystals are discussed. It is the author's belief that many more ICs, the structures of which are readily obtainable from the Cambridge Structural Database (CSD), may act as precursors to NMCs.

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“…Calixarenes, such as p - tert -butylcalix[4]arene ( 1 ) and p - tert -butylthiacalix[4]arene ( 2 ) (Chart ), are representative examples of host compounds employed in the construction of NMCs, which have “porosity without pores.” The inclusion of organic molecules and inorganic gases has been extensively investigated by the research groups of Atwood, − Ripmeester, − Gorbatchuk, − and Tsue. − Recently, molecular recognition with crystals of calixarene derivatives having channel structures has also been studied by Yamada and Hamada’s group. , Since we succeeded in achieving the selective inclusion of alcohols by crystals of compound 2 , we have extended the guest scope toward carboxylic acids, amines, and alkanes. − The crystal of compound 2 is constructed by self-inclusion dimer complexes and has no channels. We found that such an NMC with no channels can discriminate molecules of similar size and structure by the virtue of the differences in the activation energies (kinetic factor) for the inclusion and in the lattice energies (thermodynamic factor) of the resulting inclusion crystals.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Consideration for the Selective Inclusion of Disubstituted Benzene Isomers with p-tert-Butylcalix[4]arene Crystals

Matsumoto

Sasaki

Tonosaki

et al. 2021

Crystal Growth & Design

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p-tert-Butylcalix[4]arene (1) crystals can selectively include one regioisomer from a mixture of the three regioisomers for eight kinds of disubstituted benzenes. In this study, the mechanisms for the guest selectivity in the inclusion of nitrotoluene, xylene, and cresol isomers, which were chosen as representative guests showing different guest selectivity, were investigated in detail. In the competitive inclusion of three regioisomers of nitrotoluene, xylene, and cresol, crystals of compound 1 selectively include pnitrotoluene, p-xylene, and o-cresol, respectively. Time course of the change in isomer selectivity in the competitive inclusion experiment and comparison of thermogravimetric analysis profiles of the inclusion crystals with each of the isomers revealed that the selectivity for p-nitrotoluene and o-cresol was achieved under kinetic control, whereas the selectivity for p-xylene was achieved under thermodynamic control. X-ray crystallography of the inclusion crystals revealed that p-nitrotoluene and o-cresol form type A (host/ guest = 1:1) inclusion crystals, in which a guest molecule is included in the cavity of a host molecule. On the other hand, o-and mnitrotoluene and m-and p-cresol form thermodynamically stable type B (host/guest = 2:1) inclusion crystals, in which a guest molecule is included in a capsule constructed by gathering of two host molecules in a head to head manner. The selectivity for pnitrotoluene and o-cresol could be explained by the effective host−guest interaction during the formation of type A inclusion crystals, which tends to be kinetically favored over the formation of type B inclusion crystals. X-ray structure analysis and Hirshfeld surface analysis of the inclusion crystals revealed that the inclusion of xylene isomers in the crystals of compound 1 resulted in the formation of type B inclusion crystals for all the three isomers. The CH−π interaction between the two methyl groups of the p-isomer and the benzene rings of the two host molecules encapsulating the isomer is the most effective. Therefore, the inclusion crystal with p-xylene is the most stable among the three isomers, resulting in p-isomer selectivity. In this way, the crystals of compound 1 precisely distinguish different disubstituted benzene isomers under kinetic or thermodynamic control by the virtue of various host−guest interactions with the guest substituents in the cavities of type A and type B inclusion crystals.

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Azacalix[7]arene Heptamethyl Ether: Preparation, Nanochannel Crystal Structure, and Selective Adsorption of Carbon Dioxide

Cited by 48 publications

References 51 publications

CH/π hydrogen bonds in organic and organometallic chemistry

CH/π hydrogen bonds in organic and organometallic chemistry

Nanoporous molecular crystals

Mechanistic Consideration for the Selective Inclusion of Disubstituted Benzene Isomers with p-tert-Butylcalix[4]arene Crystals

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