Coordination-driven switching of a preorganized and cooperative calix[4]pyrrole receptor.

Steffen Bähring, Gunnar Olsen, Paul C Stein, Jacob Kongsted, Kent A Nielsen

Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.

Chemistry (Weinheim an der Bergstrasse, Germany) 2013 Feb 18

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The study of preorganization in receptors, particularly in cooperative receptors, and their reversible control by external stimuli is important for elucidating design strategies that can lead to increased sensitivity and external control of molecular recognition. In this work we present the design, synthesis, and operation of an asymmetric tetrathiafulvalene (TTF)-calix[4]pyrrole receptor appended with a pyridine moiety. (1)H NMR spectroscopy was employed to demonstrate that intramolecular complexation between the receptor and the pyridine moiety leads to a preorganized receptor. Absorption and (1)H NMR spectroscopy along with a computational investigation were used to demonstrate the ability of the receptor to complex the substrate 1,3,5-trinitrobenzene (TNB) and that the receptor can be reversibly modulated between negative and positive cooperativity by employing external stimuli in the form of Zn(II). Fitting procedures incorporating multiple datasets and fitting to multiple equilibria simultaneously have been employed to quantitatively determine the preorganization effects. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Citation

Steffen Bähring, Gunnar Olsen, Paul C Stein, Jacob Kongsted, Kent A Nielsen. Coordination-driven switching of a preorganized and cooperative calix[4]pyrrole receptor. Chemistry (Weinheim an der Bergstrasse, Germany). 2013 Feb 18;19(8):2768-75