Supramolecular complexes with insertion-enhanced polarity and tuned IR spectra

摘要

Extensive computational studies of structure, stability and related properties of an uncommon intermolecular system and its conformers are reported. A small organic molecule is inserted and noncovalently trapped between alkali-halide counter-ions, with their recombination prevented by significant potential energy barriers. This produces an extremely polar complex near-degenerate in energy with its dissociation asymptote and metastable relative to the conformers with the components simply attached. Two possible ways of producing such systems are indicated. Analysis of contributing interactions and dipoles, and their respective additivities is performed. Properties of the ion-molecule sub-complexes are addressed. The IR intensity spectra are simulated and exhibit a peculiar evolution upon formation of the insertion complex, facilitating its experimental detection and differentiation from other conformers. An insight into the influence of the electric field of the counter-ions on a reaction inside the system is offered.