This review addresses the synthesis of enantiopure cryptophane and the study of their chiroptical properties. Cryptophane derivatives represent an important class of macrocyclic compounds that can bind a large range of species in solution under different conditions. The overwhelming majority of these host molecules is chiral, and their chiroptical properties have been thoroughly investigated. The first part of this review is dedicated to the optical resolution and the synthesis of enantiopure cryptophane derivatives. In a second part, the study of the chiroptical properties of these molecular hosts by different techniques such as electronic and vibrational circular dichroism and Raman optical activity is detailed. These techniques allow the determination of the absolute configuration of cryptophane derivatives and provide useful information about their conformation in different conditions.
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http://dx.doi.org/10.1002/chir.23347 | DOI Listing |
Dalton Trans
November 2024
School of Chemistry, UNSW Sydney, Sydney, NSW, 2052, Australia.
Here the monocation complexes of seven -cryptophanes are examined with high-resolution ion-mobility mass spectrometry. The relative size of the [cation + cryptophane] complexes were compared based on their measured mobilities and derived collisional cross sections. A paradoxical trend of structural contraction was observed for complexes of increasing cation size.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
February 2024
Theoretical Chemistry Laboratory (LCT), Namur Institute of Structured Matter (NISM), University of Namur, 5000 Namur, Belgium.
Cryptophane molecules are cage-like structures consisting in two hemispheres, each made of three benzene rings. These hemispheres are bound together with three O(CH)Olinkers of various lengths giving rise to a plethora of cryptophane derivatives. Moreover, they are able to encapsulate neutral guests: CHCl, CHCl, …; and charged species: Cs, Tl, ….
View Article and Find Full Text PDFPhys Chem Chem Phys
August 2023
NMR Research Unit, P.O. Box 3000, FI-90014 University of Oulu, Finland.
Advances in hyperpolarisation and indirect detection have enabled the development of xenon nuclear magnetic resonance (NMR) biosensors (XBSs) for molecule-selective sensing in down to picomolar concentration. Cryptophanes (Crs) are popular cages for hosting the Xe "spy". Understanding the microscopic host-guest chemistry has remained a challenge in the XBS field.
View Article and Find Full Text PDFACS Omega
December 2022
Centre de Diffractométrie Henri Longchambon Université de Lyon 1, 5 rue la Doua, 69100 Villeurbanne, France.
We report in this article the synthesis, the X-ray crystal structure of compound -, and its binding properties with cesium and thallium in aqueous solution under basic conditions. Compound - is the diastereomeric compound of - that shows very high affinity for cesium and thallium in aqueous solution under the same conditions. Despite the close structural similarities that exist between the - and - compounds, they show large discrepancy in their ability to bind cesium and thallium cations in the same conditions.
View Article and Find Full Text PDFPhys Chem Chem Phys
August 2022
NMR Research Unit, P.O. Box 3000, FI-90014 University of Oulu, Finland.
A microscopic description of the energetics and dynamics of xenon NMR biosensors can be experimentally difficult to achieve. We conduct molecular dynamics and metadynamics simulations of a prototypical Xe@cryptophane-A biosensor in an explicit water solvent. We compute the non-covalent Xe binding energy, identify the complexation mechanism of Xe, and calculate the exchange dynamics of water molecules between the solution and the host.
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