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Probing Polyvalency in Artificial Systems Exhibiting Molecular Recognition

Fulton, David A. and Cantrill, Stuart J. and Stoddart, J. Fraser (2002) Probing Polyvalency in Artificial Systems Exhibiting Molecular Recognition. Journal of Organic Chemistry, 67 (23). pp. 7968-7981. ISSN 0022-3263. doi:10.1021/jo0110799.

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An approach to the study of polyvalencythe interaction of polyvalent receptors with polyvalent ligandsin unnatural systems is outlined. In this study, the complexation of dibenzylammonium cations by dibenzo[24]crown-8 or benzometaphenylene[25]crown-8 is utilized as the component receptor−ligand interaction. Two analogous multivalent receptorseach containing either seven dibenzo[24]crown-8 (DB24C8 CLUSTER) or seven benzometaphenylene[25]crown-8 (BMP25C8 CLUSTER) moieties appended to a modified β-cyclodextrin corewere prepared in moderate yields. For each of these multivalent receptors, complementary mono- and divalent ligands containing one or two dialkylammonium centers, respectively, were prepared in good yields. These ligands contained fluorine atom substituents to allow their interactions with crown ether compounds to be probed by ^(19)F NMR spectroscopy. The complexation of these monovalent ligands with the DB24C8 CLUSTER and the BMP25C8 CLUSTER was studied by determining the average binding constant (K_(AVE)) between the receptors and ligands. The abilities of the crown ether clusters to complex with these monovalent ligands was compared with those of the monovalent crown ethers dibenzo[24]crown-8 and benzometaphenylene[25]crown-8. In both instances, it was found that clustering seven crown ethers together into one molecule is detrimental to the abilities of the crown ether moieties to complex with monovalent dialkylammonium ligands. The complexation of the divalent ligands by the DB24C8 CLUSTER and the BMP25C8 CLUSTER was then studied again by determining K_(AVE) and their abilities to complex with these ligands was compared with those of their respective component interactions. By determining K_(AVE) for the polyvalent interaction, it was possible to calculate an association constant, K_(POLY), for the binding of the divalent ligands by the DB24C8 CLUSTER and the BMP25C8 CLUSTER compounds. In both instances K_(POLY) for the polyvalent interaction was found to be approximately 2 orders of magnitude higher than the association constants, K_A, for the component interaction.

Item Type:Article
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Cantrill, Stuart J.0000-0002-3754-7902
Stoddart, J. Fraser0000-0003-3161-3697
Additional Information:© 2002 American Chemical Society. Received 14 November 2001. Published online 24 October 2002. Published in print 1 November 2002. This research was supported by the National Science Foundation (CHE-9910199, and equipment grant CHE-9974928). We thank Dr. Peter T. Glink for all his considerable help in producing the final version of this manuscript.
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Issue or Number:23
Record Number:CaltechAUTHORS:20170426-153157256
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Official Citation:Probing Polyvalency in Artificial Systems Exhibiting Molecular Recognition David A. Fulton, Stuart J. Cantrill, and J. Fraser Stoddart The Journal of Organic Chemistry 2002 67 (23), 7968-7981 DOI: 10.1021/jo0110799
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76963
Deposited By: Ruth Sustaita
Deposited On:27 Apr 2017 16:42
Last Modified:15 Nov 2021 17:04

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