Selective Inclusion of Cyclohexanone from a Mixture with Cyclohexanol Using 1,3-Diaminocalix[4]arene Crystals

Matsumoto, Tomoaki; Hoshi, Kenta; Koyama, Ikumi; Morohashi, Naoya; Hattori, Tetsutaro

doi:10.1021/acs.cgd.3c00514

Cited by 1 publication

(1 citation statement)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Calixarene is one of the representative host molecules that afford NMCs without channel structures. Their inclusion behavior toward organic molecules and inorganic gases has been actively investigated. − We have engaged in the development of selective inclusion methods for various organic molecules with crystals of calixarene without channel structures. − For example, the selective inclusion of alcohols, , carboxylic acids, , and amines with crystals of p - tert -butylthiacalix[4]arene has been already achieved. The guest selectivity can be switched in several cases. ,, Very recently, we also reported the application using salt crystals to the selective collection of lanthanide ions from water .…”

Section: Introductionmentioning

confidence: 99%

Selective Inclusion of Cyclohexanediol Stereoisomer by Crystals of Open-Chain Diol-Type Host Based on a Partial Structure of p-tert-Butylthiacalixarene

Morohashi,

Suzuki,

Ogihara

et al. 2024

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

For the efficient separation of hard-to-separate organic molecule isomers, the creation of solid materials that can distinguish between isomers and selectively collect them is important. For example, in the separation of organic molecule isomers that have multiple functional groups such as hydroxy groups, the design of host molecules that allow the precise recognition of the positions and orientations of the functional groups is required. In this study, based on sulfur-bridged phenol dimer that is a partial structure of p-tert-butylthiacalixarene, an open-chain diol-type host 2 was designed and synthesized. In compound 2, two phenolic hydroxy groups were bridged with a methylene group to fix the conformation, and two alcoholic hydroxy groups were introduced for guest recognition sites. In a competitive inclusion experiment from an aqueous solution of a cis/trans mixture of 1,3-cyclohexanediol, crystals of host 2 selectively included cis-isomer. The isomer selectivity was low for the inclusion of 1,2-diol, and 1,4-diol was not included. X-ray crystallographic analysis of the inclusion complex of host 2, which predominantly included the cis-isomer of 1,3-diol, revealed that two hydroxy groups of the host form cooperative hydrogen bonds with two hydroxy groups of the guest. The results show that densely packed stable crystals can be formed by fixing the conformation of the host to construct an inclusion space and by the precise recognition of the guest functional groups complementary to the host molecule. This study provides an approach for the design of host molecules that can selectively include difficult-to-separate target molecules.

show abstract