Small Molecule Regulation of Self-Association and Catalytic Activity in a Supramolecular Coordination Complex
Author
McGuirk, C. Michael
Stern, Charlotte L.
Mirkin, Chad A.
Date
2014Metadata
Show full item recordAbstract
Herein, we report the synthesis and characterization of the first
weak-link approach (WLA) supramolecular construct that employs the small
molecule regulation of intermolecular hydrogen bonding interactions for the in situ
control of catalytic activity. A biaryl urea group, prone to self-aggregation, was
functionalized with a phosphinoalkyl thioether (P,S) hemilabile moiety and
incorporated into a homoligated Pt(II) tweezer WLA complex. This urea-containing
construct, which has been characterized by a single crystal X-ray diffraction study,
can be switched in situ from a rigid fully closed state to a flexible semiopen state via
Cl− induced changes in the coordination mode at the Pt(II) structural node. FT-IR
and 1H NMR spectroscopy studies were used to demonstrate that while extensive
urea self-association persists in the flexible semiopen complex, these interactions are
deterred in the rigid, fully closed complex because of geometric and steric restraints.
Consequently, the urea moieties in the fully closed complex are able to catalyze a
Diels-Alder reaction between cyclopentadiene and methyl vinyl ketone to generate
2-acetyl-5-norbornene. The free urea ligand and the semiopen complex show no such activity. The successful incorporation and
regulation of a hydrogen bond donating catalyst in a WLA construct open the doors to a vast and rapidly growing catalogue of
allosteric catalysts for applications in the detection and amplification of organic analytes.
Description
The article of record as published may be found at http://dx.doi.org/10.1021/ja500214r
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