Increasing the accuracy and computational applicability of electronic structure calculations is a primary objective in computational quantum chemistry. Density functional theory (DFT) has traditionally been the method of choice for most quantum chemical applications involving large molecules. The direct application of more accurate wave-function-based methods including higher order electron correlation effects has been a computational bottleneck for large molecules. To overcome these limitations, we have developed fragment-based methods to compute accurate energies and properties of large molecules. In this talk, we explore the application of DFT methods as well as our multilayer Molecules-in-Molecules (MIM) fragment-based method for the study of the energies in supramolecular systems, viz. macrocycles, foldamers, cages, and their anion-bound complexes. We provide an assessment of the performance of different models for the determination of the binding affinities of a range of macrocycle-anion and foldamer-anion complexes in a variety of nonpolar as well as polar solvent environments. In addition, the binding of small and large anions with single and double-helical receptors, and the associated size-related modulations will be described. Finally, the use of cages as efficient anion receptors for extraction will be explored.

Computational approaches for supramolecular interaction energies: Macrocycles, foldamers, cages, and their complexes with anions

ACS Spring 2022

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