Different and Often Opposing Forces Drive the Encapsulation and Multiple Exterior Binding of Charged Guests to a M 4 L 6 Supramolecular Vessel in Water

Sgarlata, Carmelo; Mugridge, Jeffrey S.; Pluth, Michael D.; Zito, Valeria; Arena, Giuseppe; Raymond, Kenneth N.

doi:10.1002/chem.201703202

Title: Different and Often Opposing Forces Drive the Encapsulation and Multiple Exterior Binding of Charged Guests to a M ₄ L ₆ Supramolecular Vessel in Water

Journal Article · Wed Nov 08 00:00:00 EST 2017 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201703202· OSTI ID:1408154

Sgarlata, Carmelo ^[1]; Mugridge, Jeffrey S. ^[1]; Pluth, Michael D. ^[1]; Zito, Valeria ^[2]; Arena, Giuseppe ^[3];

^[1]

Department of Chemistry University of California, Berkeley and Chemical Science Division, Lawrence Berkeley National Laboratory Berkeley California 94720-1460 USA
Istituto di Biostrutture e Bioimmagini CNR, UOS Catania Via P. Gaifami 18 95125 Catania Italy
Dipartimento di Scienze Chimiche Università degli Studi di Catania Viale A. Doria 6 95125 Catania Italy

Abstract The supramolecular assembly [Ga ₄ L ₆ ] ¹²⁻ acts as a nanoscale flask to mediate the reactivity of encapsulated reactive guests and also functions as a catalyst to carry out enzyme‐like chemical transformations. The guest binding to the interior cavity and exterior of this host is difficult to untangle because multiple equilibria occur in solution, and only when refining simultaneously data obtained from different techniques, such as NMR, UV/Vis, and calorimetry, can the accurate solution thermodynamics of these host–guest systems be determined. This study reports the driving forces for the inclusion and stepwise exterior guest binding of different aliphatic quaternary ammonium guests to the [Ga ₄ L ₆ ] ¹²⁻ assembly. Encapsulation into the host cavity was found to be an entropy‐driven process, whereas exterior ion association is driven either by enthalpically favorable attractive forces or by the entropy gain due to desolvation, depending on guest size and character. The analysis of the energetics of reaction may help predicting and understanding the intimate role and contribution of the transition state in those rate‐accelerated reactions involving this supramolecular assembly as an enzyme‐like molecular flask.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1408154

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Vol. 23 Journal Issue: 66; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 14 works

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Title: Different and Often Opposing Forces Drive the Encapsulation and Multiple Exterior Binding of Charged Guests to a M ₄ L ₆ Supramolecular Vessel in Water