A Self-Folding Metallocavitand

A Self-Folding Metallocavitand

The synthesis and characterization of novel metallocavitand 6 are described. This is a covalent hybrid of a deepened, self-folding cavity and a Zn−phenanthroline fragment. Host 6 features a large molecular cavity of ∼8 × 10 Å dimensions, and the metal binding site is directed in toward the cavity. B...

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Veröffentlicht in:Journal of the American Chemical Society 2001-10, Vol.123 (41), p.9929-9934
Hauptverfasser: Lücking, Ulrich, Chen, Jian, Rudkevich, Dmitry M, Rebek, Julius
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Sprache:eng
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Hydrogen Bonding
Magnetic Resonance Spectroscopy
Molecular Conformation
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
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container_end_page 9934
container_issue 41
container_start_page 9929
container_title Journal of the American Chemical Society
container_volume 123
creator Lücking, Ulrich
Chen, Jian
Rudkevich, Dmitry M
Rebek, Julius
description The synthesis and characterization of novel metallocavitand 6 are described. This is a covalent hybrid of a deepened, self-folding cavity and a Zn−phenanthroline fragment. Host 6 features a large molecular cavity of ∼8 × 10 Å dimensions, and the metal binding site is directed in toward the cavity. Binding abilities of the metallocavitand in solution was demonstrated for quinuclidine 11 and Dabco 12 using UV−vis and 1H NMR spectroscopy. Intramolecular hydrogen bonds at the upper rims of cavitand 6 resist the unfolding of the inner cavities and thereby increase the energetic barrier to guest exchange. The exchange is slow on the NMR time scale (at ambient temperatures, CD2Cl2), and kinetically stable complexes result. Both the polyaromatic cavity and metallosite participate simultaneously in the binding event. Zinc-containing deep cavities may be attractive as catalytic chambers for hydrolysis and esterification.
doi_str_mv 10.1021/ja011488m
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subjects Hydrogen Bonding
Magnetic Resonance Spectroscopy
Molecular Conformation
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
title A Self-Folding Metallocavitand
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