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Effect of Lower‐Rim Alkylation of p ‐Sulfonatocalix[4]arene on the Thermodynamics of Host–Guest Complexation
Author(s) -
Cui Jie,
Uzunova Vanya D.,
Guo DongSheng,
Wang Kui,
Nau Werner M.,
Liu Yu
Publication year - 2010
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200901361
Subject(s) - chemistry , isothermal titration calorimetry , enthalpy , calixarene , aqueous solution , molecule , host–guest chemistry , calorimetry , titration , supramolecular chemistry , crystallography , selectivity , computational chemistry , thermodynamics , organic chemistry , physics , catalysis
The complex stability constants ( K S ) and thermodynamic parameters (Δ H ° and T Δ S °) for the 1:1 complexation of two water‐soluble calixarenes, p ‐sulfonatocalix[4]arene (SC4A) and 5,11,17,23‐tetrasulfonato‐25,26,27,28‐tetrakis( n ‐butyl)calix[4]arene (SC4A‐Bu), with organic ammonium cations and neutral spherical organic molecules, have been determined by means of isothermal titration calorimetry (ITC) in aqueous solutions at 298.15 K. The obtained results indicate that, upon complexation with these guests by SC4A‐Bu, the enthalpy changes become less favorable, whereas the entropy changes become more favorable relative to SC4A complexation. These differences can be attributed to differential degrees of desolvation and removal of high‐energy water as well as the change in conformation or conformational degrees of freedom upon complexation. The calorimetric investigations, accompanied by 1 H NMR and UV/Vis spectroscopy and X‐ray crystallography provide a thermodynamic explanation for the different complexation behavior of SC4A and SC4A‐Bu towards charged and neutral organic guests. Binding ability and molecular selectivity are discussed from the viewpoint of the conformational geometry and electronic properties of hosts and guests.