Cryptophanes for Methane and Xenon Encapsulation: A Comparative Density Functional Theory Study of Binding Properties and NMR Chemical Shifts

The host-guest chemistry of cryptophanes is an active research area because of its applications in sensor design, targeting small molecules and atoms in environmental and medical sciences. As such, the computational prediction of binding energies and nuclear magnetic resonance (NMR) properties of different cryptophane complexes are of interest to both theoreticians and experimentalists working in host guest based sensor development. Herein we present a study of 10 known and some newly proposed cryptophanes using density functional theory (DFT) calculations. We benchmark the description of nonbonding interactions by different DFT functionals against spin-component-scaled, second-order Moller Plesset theory (SCS-MP2) and predict novel host molecules with enhanced affinity toward methane and Xenon, two representative systems of high interest. We demonstrate the power and limitations of the different computational methods in describing the binding and NMR properties of these established and novel host systems. The results show the importance of including dispersion corrections in the DFT functionals. The overall analysis of the dispersion corrections indicated that results obtained from pure DFT functionals should be used cautiously when conclusions are drawn for molecular systems with considerable weak interactions. Proposed analogues of cryptophane-A, where the alkoxy bridges are replaced by alkyl chains, are predicted to display enhanced affinity toward both methane and Xenon.