Host‐Guest Complexation Between Cyclodextrins and Hybrid Hexavanadates: What are the Driving Forces?
- 14 September 2021
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 27 (62), 15516-15527
- https://doi.org/10.1002/chem.202102684
Abstract
Host-guest complexes between native cyclodextrins (α-, β- and γ-CD) and hybrid Lindqvist-type polyoxovanadates (POVs) [V6O13((OCH2)3C-R)2]2– with R=CH2CH3, NO2, CH2OH and NH(BOC) were studied in aqueous solution. 6 crystal structures determined by SCXRD analysis revealed the nature of the R group strongly influences the host–guest conformation. In all systems isolated in the solid-state, the organic groups R are embedded within the CD cavities, involving only a few weak supramolecular contacts. The interaction between hybrid POVs and the macrocyclic organic hosts have been studied in solution using ITC, cyclic voltammetry and NMR methods (1H NMR, and 2D DOSY, and ROESY). This set of complementary techniques provides clear insights about the strength of interactions and the binding host-guest modes occurring in aqueous solution, highlighting a dramatic influence of the functional group R on the supramolecular properties of the POV (association constant K1:1 vary from 0 to 2 000 M-1 ) while isolated functional organic groups exhibit only very weak intrinsic affinity with CDs. Electrochemical and calorimetric investigations suggest that the driving force of the host-guest association involving larger CDs (β- and γ-CD) is mainly related to the chaotropic effect. In contrast, the hydrophobic effect supported by weak attractive forces appears as the main contributor for the formation of α-CD-containing host-guest complexes. In any cases, the origin of driving forces is clearly related to the ability of the macrocyclic host to desolvate the exposed moieties of the POVs.This publication has 55 references indexed in Scilit:
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