Chemical Shielding Anisotropies for Chloroform Exchanging between a Free Site and a Complex with Cryptophane-D: A Cross-Correlated NMR Relaxation Study

Abstract

The case of (13)C-labeled chloroform exchanging between a free site in solution and the encaged site within the cryptophane-D cavity is investigated using the measurements of longitudinal cross-correlated relaxation rates, involving the interference of the dipole-dipole and chemical shielding anisotropy interactions. A compact theoretical expression is provided, along with an experimental protocol, based on INEPT (insensitive nuclei enhanced by polarization)-enhanced double-quantum-filtered inversion recovery measurements. The analysis of the build-up curves results in a set of cross-correlated relaxation rates for both the (13)C and (1)H spins at the two sites. It is demonstrated that the results can be given a consistent interpretation in terms of molecular-level properties, such as rotational correlation times, the Lipari-Szabo order parameter, and interaction strength constants. The analysis yields the bound-site carbon-13 chemical shielding anisotropy, ΔσC = -58 ± 8 ppm, in good agreement with most recent liquid-crystal measurements and the corresponding proton shielding anisotropy, ΔσH = 14 ± 2 ppm.

Access to the Syn diastereomers of cryptophane cages using HFIP

“…These cryptophanes could be used like cryptophane A for the encapsulation of xenon, 25 but they are most specifically known for their binding properties with chloroform. 26–28 The improved yield in the synthesis syn -cryptophane D prompted us to test the HFIP/KHSO 4 combination for the synthesis of other cryptophanes.…”