Host–Guest Exchange of Viologen Guests in Porphyrin Cage Compounds as Studied by Selective Exchange Spectroscopy (1D EXSY) NMR

• Published in: Angewandte Chemie International Edition Vol. 60; no. 3; pp. 1254 - 1262
• Main Authors: Swartjes, Anne, White, Paul B., Lammertink, Marijn, Elemans, Johannes A. A. W., Nolte, Roeland J. M.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 18-01-2021; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: 1D EXSY NMR; Binding; Cage compounds; Entropy of activation; Foreign exchange rates; host–guest exchange; kinetics; Magnetic resonance spectroscopy; NMR; NMR spectroscopy; Nuclear magnetic resonance; Polymers; Porphyrins; porphyrins cage; Rate constants; Spectroscopy; Spectrum analysis; Supramolecular compounds; viologen guest; porphyrins cage; host-guest exchange; 1D EXSY NMR; kinetics; viologen guest
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202010335

Dynamics in complexes of porphyrin cage compounds and viologen‐derived guest molecules are investigated by selective exchange NMR spectroscopy (1D EXSY). Exchange rates were found to be independent of excess guest concentration, revealing a dissociative exchange mechanism, which is accompanied by negative activation entropies, indicating significant reorganization of the host–guest complex during dissociation. Nonsymmetric viologen guests with bulky head groups had more unidirectional binding and slower exchange rates than guests with less‐bulky head groups. Thermodynamic and kinetic studies revealed that the exchange process is primarily driven by the thermodynamics of binding and that guest binding can be influenced by introducing steric and electronic groups on the host . Exchange studies with guests bearing a polymer chain revealed that both slippage and full dissociation takes place and the rate constants for both processes were determined. The slippage rate constant revealed that for smaller guests exchange takes place nearly exclusively under thermodynamic control.
Dynamics in complexes of porphyrin cage compounds and viologen‐derived guest molecules are investigated by selective exchange NMR spectroscopy (1D EXSY). These studies explore the mechanism of host–guest exchange, how steric and electronic properties influence the rate of exchange, and whether the exchange process is governed by kinetic or thermodynamic factors.