Selective Self-Organization of Guest Molecules in Self-Assembled Molecular Boxes

This article describes the synthesis and binding properties of highly selective noncovalent molecular receptors 1 3·(DEB)6 and 3 3·(DEB)6 for different hydroxyl functionalized anthraquinones 2. These receptors are formed by the self-assembly of three calix[4]arene dimelamine derivative molecules (1...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2005-09, Vol.127 (36), p.12697-12708
Main Authors: Kerckhoffs, Jessica M. C. A, ten Cate, Mattijs G. J, Mateos-Timoneda, Miguel A, van Leeuwen, Fijs W. B, Snellink-Ruël, Bianca, Spek, Anthony L, Kooijman, Huub, Crego-Calama, Mercedes, Reinhoudt, David N
Format: Article
Language:English
Subjects:
Anthraquinones - chemistry
Barbiturates - chemistry
Calixarenes - chemical synthesis
Calixarenes - chemistry
Chemistry
Crystallography, X-Ray
Exact sciences and technology
General and physical chemistry
Models, Molecular
Molecular Structure
Phenols - chemical synthesis
Phenols - chemistry
Solution properties
Solutions
Triazines - chemical synthesis
Triazines - chemistry
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Summary:This article describes the synthesis and binding properties of highly selective noncovalent molecular receptors 1 3·(DEB)6 and 3 3·(DEB)6 for different hydroxyl functionalized anthraquinones 2. These receptors are formed by the self-assembly of three calix[4]arene dimelamine derivative molecules (1 or 3) and six diethylbarbiturate (DEB) molecules to give 1 3·(DEB)6 or 3 3·(DEB)6. Encapsulation of 2 occurs in a highly organized manner; that is, a noncovalent hydrogen-bonded trimer of 2 is formed within the hydrogen-bonded receptors 1 3·(DEB)6 and 3 3·(DEB)6. Both receptors 1 3·(DEB)6 and 3 3·(DEB)6 change conformation from staggered to eclipsed upon complexation to afford a better fit for the 2 3 trimer. The receptor selectivity toward different anthraquinone derivatives 2 has been studied using 1H NMR spectroscopy, X-ray crystallography, UV spectroscopy, and isothermal microcalorimetry (ITC). The π−π stacking between the electron-deficient center ring of the anthraquinone derivatives 2a−c and 2e−g and the relatively electron-poor melamine units of the receptor is the driving force for the encapsulation of the guest molecules. The selectivity of the hydrogen-bonded host for the anthraquinone derivatives is the result of steric interactions between the guest molecules and the calix[4]arene aromatic rings of the host.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0536973