Cryptophanes and Their Complexes—Present and Future

Brotin, Thierry; Dutasta, Jean‐Pierre

doi:10.1021/cr0680437

Cited by 383 publications

(362 citation statements)

References 162 publications

(394 reference statements)

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“…The occurrence of one C 3 -symmetric set of signals for impl-1 can either mean that impl-1 adopts a C 3 -symmetric in-out conformation or that it exhibits a C 1 -symmetric out-saddle conformation 12 which leads to a C 3 -symmetric spectrum owing to pseudorotation 27 . The latter conformation has already been described for cryptophane-A derivatives and larger cryptophanes 16,28,29 .…”

Section: Determinationmentioning

confidence: 99%

“…For binding such guests cage compounds are most suitable as they are able to fully enclose molecules and thereby increase the quantity of dispersion interactions [7][8][9] . Prominent examples for cage compounds are cryptophanes [10][11][12] . Cryptophanes are composed of two bowlshaped cyclotriveratrylene (CTV) subunits connected by three aliphatic linker groups, thus forming an interior cavity.…”

mentioning

confidence: 99%

“…Cryptophanes are composed of two bowlshaped cyclotriveratrylene (CTV) subunits connected by three aliphatic linker groups, thus forming an interior cavity. Numerous studies have been published which deal with the reversible binding of cryptophane hosts to small nonpolar molecules 12 . Interaction intensities and thus binding constants are highly dependent on the size and shape of the guests and host cavities.…”

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confidence: 99%

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Strongly underestimated dispersion energy in cryptophanes and their complexes

2014

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Cryptophanes, composed of two bowl-shaped cyclotriveratrylene subunits linked by three aliphatic linker groups, are prototypal organic host molecules which bind reversibly neutral small guest compounds via London forces. The binding constants for these complexes are usually measured in tetrachloroethane and are in the range of 10 2 -10 3 M À 1 . Here we show that tetrachloroethane is-in contrast to the scientific consensus-enclosed by the cryptophane-E cavity. By means of NMR spectroscopy we show that the binding constant for CHCl 3 @cryptophane-E is in larger solvents two orders of magnitudes higher than the one measured before. Ab initio calculations reveal that attractive dispersion energy is responsible for high binding constants and for the formation of imploded cryptophanes which seem to be more stable than cryptophanes with empty cavities.

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Section: Determinationmentioning

confidence: 99%

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Strongly underestimated dispersion energy in cryptophanes and their complexes

2014

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“…Stable isotope 129 Xe has a spin-half nucleus that can be hyperpolarized to generate very large signals for MRI (3). Host molecules have been identified that bind xenon with high affinity (4), motivating further technological applications. Much less studied is radon, a radioactive noble gas that occurs as an intermediate species in the decay chain of uranium-238, an element ubiquitous in Earth's crust.…”

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confidence: 99%

Measurement of radon and xenon binding to a cryptophane molecular host

Jacobson

Khan²,

Collé³

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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Xenon and radon have many similar properties, a difference being that all 35 isotopes of radon ( 195 Rn– 229 Rn) are radioactive. Radon is a pervasive indoor air pollutant believed to cause significant incidence of lung cancer in many geographic regions, yet radon affinity for a discrete molecular species has never been determined. By comparison, the chemistry of xenon has been widely studied and applied in science and technology. Here, both noble gases were found to bind with exceptional affinity to tris-(triazole ethylamine) cryptophane, a previously unsynthesized water-soluble organic host molecule. The cryptophane–xenon association constant, K a = 42,000 ± 2,000 M -1 at 293 K, was determined by isothermal titration calorimetry. This value represents the highest measured xenon affinity for a host molecule. The partitioning of radon between air and aqueous cryptophane solutions of varying concentration was determined radiometrically to give the cryptophane–radon association constant K a = 49,000 ± 12,000 M -1 at 293 K.

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“…[1][2][3] CTV itself can complex fullerenes or other globular molecular guests within its hydrophobic cavity. Moreover, other functionalities can be appended onto the CTV scaffold by derivatization of its methoxy groups, allowing organic [2][3][4][5] and metal-organic 2,6,7 cage compounds, frameworks and other supramolecular assemblies 8 based on the CTV moiety to be constructed. Recently, we 9,10 and others 11,12 have extended the chemistry of CTV by preparing thiolated analogues 1 and 2 (Scheme 1).…”

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confidence: 99%

Hexasulfanyl analogues of cyclotriveratrylene

Little

Loughrey

Santoro

et al. 2014

Tetrahedron Letters

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The synthesis of four 3,4-di(alkylsulfanyl)benzyl alcohol derivatives is described, in five steps from methyl 3,4-di(hydroxy)benzoate via a Newman-Kwart rearrangement. Incubation of these derivatives in formic acid affords 2,3,7,8,12,13-hexakis(alkylsulfanyl)-10,15-dihydro-5H-tribenzo[a,d,g]cyclononene products, which are hexa-sulfanyl analogues of the wellknown supramolecular cavitand host, cyclotriveratrylene (CTV). The yield of this cyclization depends strongly on the alkylsulfanyl substituents present, in the order SMe > SEt ≈ SiPr >> SBn. A crystal structure determination of one of the cyclotrimers shows a mode of self-association that is commonly exhibited by CTV itself.

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Cryptophanes and Their Complexes—Present and Future

Cited by 383 publications

References 162 publications

Strongly underestimated dispersion energy in cryptophanes and their complexes

Strongly underestimated dispersion energy in cryptophanes and their complexes

Measurement of radon and xenon binding to a cryptophane molecular host

Hexasulfanyl analogues of cyclotriveratrylene

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