Inclusion of Alkanes with a Crystal Consisting of Exocavity Complexes of <i>p-tert-</i>Butylthiacalix[4]arene with Diethylamine: Extension of Guest Scope by Changing the Structure of Inclusion Crystals

Morohashi, Naoya; Miyoshi, Ikuko; Sasaki, Tomoya; Nakaji, Yosuke; Hiroko, Nakayama; Hattori, Tetsutaro

doi:10.1021/acs.cgd.9b00837

Cited by 15 publications

(7 citation statements)

References 54 publications

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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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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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“…This gives an additional dimension to molecular recognition of guest compounds using the same host. For example, for thiacalix [4]arene (Galyaltdinov et al, 2014) and tert-butylthiacalix[4]arene (Galyaltdinov et al, 2012;Morohashi et al, 2019), the guest exchange increases the range of included compounds thus decreasing the inclusion selectivity. Still, this selectivity remains essentially stepwise.…”

Section: Selectivity Of Guest Exchange In Inclusion Compoundmentioning

confidence: 99%

Smart Molecular Recognition: From Key-to-Lock Principle to Memory-Based Selectivity

2020

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The formation and decomposition of inclusion compounds with a solid-solid phase transition may be very selective to the guest molecular structure. This selectivity may function in essentially different ways than defined by the classical concept of molecular recognition, which implies the preferential binding of complementary molecules. Solid inclusion compounds may take part as an initial or/and final state in several processes of different types summarized in this review, which selectivity is boosted by cooperativity of participating molecular crystals. Some of these processes resemble switching electronic devices and can be called smart giving practically absolute molecular recognition.

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“…Calixarene, such as p - tert -butylcalix[4]arene ( 1 ) or p - tert -butylthiacalix[4]arene ( 2 ) (Chart ), is a typical host molecule that gives NMC having no empty channel structures, − whereas most NMCs form clathrate-type inclusion crystals in which the guest compound is included in the lattice constructed by the host compound. − The inclusion behavior of organic molecules and inorganic gases with crystals of calixarenes has been widely studied by the research groups of Atwood, − Ripmeester, − Gorbatchuk, − and Tsue. − Recently, the recognition of organic molecules with crystals of thiacalix[4]arene derivatives having channel structures has also been studied by Yamada and Hamada’s group. , Achieving the selective inclusion of alcohol using the crystals of compound 2 , we have developed selective inclusion methods for various organic molecules. − Calixarene crystals can construct complex-type inclusion crystals consisting of discrete host–guest complexes, accompanied by structural changes. Therefore, the difference between guest structures is easily reflected in the difference between the thermal stabilities of the crystal structures (thermodynamic control) and their activation energies during phase transition, which can also be used to introduce selectivity (kinetic control).…”

Section: Introductionmentioning

confidence: 99%

Switching of Guest Selectivity for the Inclusion of Regioisomers of Monosubstituted Phenols with Crystals of p-tert-Butylcalix[4]arene

Morohashi

Sakamoto

Matsumoto

et al. 2023

Crystal Growth & Design

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To develop an inclusion method for hard-to-separate organic molecules with wide guest scopes, we examined the control of guest selectivity via external factors such as solvents, temperature, and additives for the competitive inclusion of monosubstituted phenol isomers with crystals of p-tert-butylcalix[4]arene 1. Guest selectivity was thus switched between two isomers in the inclusion of cresol, fluorophenol, and bromophenol and between three isomers in the inclusion of chlorophenol. The mechanism of guest selectivity in chlorophenol inclusion was mainly determined using X-ray crystal structural analysis and a comparison of the thermal stabilities and the formation rates of inclusion crystals with each isomer. Under kinetic control, the inclusion from decane at a low temperature selectively yielded type-A (host/guest = 1:1) inclusion crystals of p-isomer (1·p-chlorophenol) in which the host and guest molecules exhibited CH−π and OH–π interactions. In aqueous solutions at high temperatures, where water molecules inhibited the inclusion of m-isomer, thermally stable type-B (host/guest = 2:1) crystals of o-isomer (1 2·o-chlorophenol), in which a guest molecule was included in a capsule constructed by two host molecules, selectively formed. Furthermore, the inclusion from decane in the presence of methanol produced a co-inclusion crystal of type-C (host/guest/additive = 2:1:1) in which a 1:1 complex of m-isomer and methanol, connected via an intermolecular hydrogen bond, was selectively included by the distorted capsule of two host molecules to form 1 2·m-chlorophenol·CH3OH.

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Inclusion of Alkanes with a Crystal Consisting of Exocavity Complexes of p-tert-Butylthiacalix[4]arene with Diethylamine: Extension of Guest Scope by Changing the Structure of Inclusion Crystals

Cited by 15 publications

References 54 publications

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

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

Smart Molecular Recognition: From Key-to-Lock Principle to Memory-Based Selectivity

Switching of Guest Selectivity for the Inclusion of Regioisomers of Monosubstituted Phenols with Crystals of p-tert-Butylcalix[4]arene

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