Highly selective molecular sieving of <i>cis</i>- over <i>trans</i>-1,2-dichloroethene isomers

Liu, Xin; Alimi, Lukman O.; Khashab, Niveen M.

doi:10.1039/d2cc03574j

Cited by 12 publications

(19 citation statements)

References 34 publications

(39 reference statements)

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“…Only recently, Chaix, He, , Dey, − Liu, Ding, and co-workers have proven the ability of macrocyclic chiral polyimines to selectively capture gases or to recognize and separate small organic molecules. − However, only little is known about the similar properties of the reduced counterparts of macrocyclic polyimines. This is apparently due to much higher structural dynamics of polyamines resulting in the adaptation of different conformations by the given macrocycle .…”

Section: Introductionmentioning

confidence: 99%

“…23 In some cases, the poor shape complementarities lead to obtaining the supramolecular organic frameworks (SOFs), characterized by intrinsic permanent porosity. 24−29 Only recently, Chaix, 30 He, 18,31 Dey, 32−34 Liu, 35 Ding, 36 and co-workers have proven the ability of macrocyclic chiral polyimines to selectively capture gases or to recognize and separate small organic molecules. 37−40 However, only little is known about the similar properties of the reduced counterparts of macrocyclic polyimines.…”

Section: ■ Introductionmentioning

confidence: 99%

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Unravelling Structural Dynamics, Supramolecular Behavior, and Chiroptical Properties of Enantiomerically Pure Macrocyclic Tertiary Ureas and Thioureas

2022

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The introduction of urea or thiourea functionality to the macrocycle skeleton represents an alternative way to control conformational dynamics of chiral, polyamines of a figure-shaped periodical structure. Formally highly symmetrical, these macrocycles may adapt diverse conformations, depending on the nature of an amide linker and on a substitution pattern within the aromatic units. The type of heteroatom X in the N−C(�X)−N units present in each vertex of the macrocycle core constitutes the main factor determining the chiroptical properties. In contrast to the urea-containing derivatives, the electronic circular dichroism of thioureas is controlled by the chiral neighborhood closest to the chromophore. The dynamically induced exciton couplet is observed when the biphenyl chromophores are present in the macrocycle core. In the solid state, the seemingly disordered molecules may create ordered networks stabilized by intermolecular S•••halogen, H•••halogen, and S•••H interactions. The presence of two bromine substituents in each aromatic unit in thiourea-derived trianglamine gives rise to a self-sorting phenomenon in the crystal. In solution, this particular macrocycle exists as a dynamic equimolar mixture of two conformational diastereoisomers, differing in the spatial (clockwise and counter clockwise) arrangement of the C−Br bonds. In the crystal lattice, macrocycles of a given handedness assemble into homohelical layers.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Unravelling Structural Dynamics, Supramolecular Behavior, and Chiroptical Properties of Enantiomerically Pure Macrocyclic Tertiary Ureas and Thioureas

2022

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“…In 2022, the Khashab group described a porous trianglimine macrocycle ( NaTI ) that was also capable of selectively separating cis -DCE from an equimolar cis - and trans - DCE mixture with a purity of over 96% using the host cavity . Selectivity was ascribed to effective host–guest C–H···π intermolecular interactions.…”

Section: Hydrocarbon Separationsmentioning

confidence: 99%

Industrial Separation Challenges: How Does Supramolecular Chemistry Help?

Zhang,

Lin,

Huang

et al. 2023

J. Am. Chem. Soc.

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The chemical industry and the chemical processes underscoring it are under intense scrutiny as the demands for the transition to more sustainable and environmentally friendly practices are increasing. Traditional industrial separation systems, such as thermally driven distillation for hydrocarbon purification, are energy intensive. The development of more energy efficient separation technologies is thus emerging as a critical need, as is the creation of new materials that may permit a transition away from classic distillation-based separations. In this Perspective, we focus on porous organic cages and macrocycles that can adsorb guest molecules selectively through various host−guest interactions and permit molecular sieving behavior at the molecular level. Specifically, we summarize the recent advances where receptor-based adsorbent materials have been shown to be effective for industrially relevant hydrocarbon separations, highlighting the underlying host−guest interactions that impart selectivity and permit the observed separations. This approach to sustainable separations is currently in its infancy. Nevertheless, several receptor-based adsorbent materials with extrinsic/intrinsic voids or special functional groups have been reported in recent years that can selectively capture various targeted guest molecules. We believe that the understanding of the interactions that drive selectivity at a molecular level accruing from these initial systems will permit an ever-more-effective "bottom-up" design of tailored molecular sieves that, in due course, will allow adsorbent material-based approaches to separations to transition from the laboratory into an industrial setting.

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“…Of particular interest are those trianglamines in which the macrocyclic skeleton has been rigidified either by N,N′-bridging or protonation, as this allows their inner cavity to be controlled. As a result, these shape-persistent trianglamines are increasingly being examined for their ability to selectively adsorb and separate in the gas and liquid phase [14][15][16][17][18] or to act as supergelators. 19 These observations have prompted us to investigate a bridged trianglamine in which one of the equivalent hydrogen atoms of a methylene group is replaced by an alkyl or aryl substituent.…”

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confidence: 99%

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confidence: 99%

Symmetry-driven diastereoselective functionalization of simple trianglamine

et al. 2022

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Highly selective molecular sieving of cis- over trans-1,2-dichloroethene isomers

Abstract: An intrinsically porous trianglimine macrocycle 1 is reported to display energy-efficient and cost-effective adsorptive properties by selectively separating cis-1,2-dichloroethene (cis-DCE) from an equimolar cis- and trans-DCE mixture with a purity...

Cited by 12 publications

References 34 publications

Unravelling Structural Dynamics, Supramolecular Behavior, and Chiroptical Properties of Enantiomerically Pure Macrocyclic Tertiary Ureas and Thioureas

Unravelling Structural Dynamics, Supramolecular Behavior, and Chiroptical Properties of Enantiomerically Pure Macrocyclic Tertiary Ureas and Thioureas

Industrial Separation Challenges: How Does Supramolecular Chemistry Help?

Symmetry-driven diastereoselective functionalization of simple trianglamine

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