Enantiomerenreine wasserlösliche [Fe₄L₆]‐Käfigverbindungen: Wirt‐Gast‐Chemie und katalytische Aktivität

Abstract

Wir danken dem Schweizerischen Nationalfonds (SNF) und dem Europäischen Forschungsrat (ERC) für die finanzielle Unterstützung. Dank gilt auch dem EPSRC Mass Spectrometry Service in Swansea für die Durchführung der FT-ICR-MS-Experimente. Hintergrundinformationen zu diesem Beitrag sind im WWW unter http://dx.

Self‐Assembly of Functional Discrete Three‐Dimensional Architectures in Water

“…[82] In order to achieve water solubility of af amily of terphenylene-based tetrahedral cages,t hat had previously been reported to assemble in acetonitrile, [83] Nitschke and coworkers installed chiral glyceryl groups on the central phenyl ring of the terphenyl ligand. [84] These glyceryl groups closed the faces of the tetrahedral cage,c reating am ore shielded hydrophobic cavity.Alarge set of potential guest molecules was screened for binding inside this hydrophobic cavity,w hich had an estimated volume of more than 400 3 .T he size of the guest was found to be the major parameter dictating the binding behaviour.F rom ac atalysis point of view,i ti sw orthwhile to point out that the enantiopure cage Figure 6. Single-crystal X-ray structure (A) of the prismatic cage 9,t hat can catalyse the Michael addition reaction of nitro-olefins(B, top), as well as the Diels-Alderreaction of 9-hydroxymethylanthracene (B, bottom).…”

Coordination‐Cage‐Catalysed Hydrolysis of Organophosphates: Cavity‐ or Surface‐Based?

“…Indeed there have been af ew other reports of catalysed destruction of organophosphates in the cavities of am etal-organic [10a, b] and covalent organic [10c] frameworks, and at etrahedral coordination cage. [11] We have reported recently the binding of a range of alkyl phosphonates-relatively unreactive andb enign simulants of G-series chemical warfarea gents-in the cavity of one of our cages in water, [12] and this work follows on from that but exploits the catalytic activity of the cages to destroy the more reactive phosphotriester substrates. In the course of this work we have discovered-entirely unexpectedly-thati t is not necessary for the substrates to be bound inside the cavity for catalysed hydrolysis to occur,b ut that observable catalysis can occur at the external surface, albeit with less efficiency than occurred in the Kemp elimination reaction of a cavity-bound substrate.…”

A Supramolecular Sorting Hat: Stereocontrol in Metal–Ligand Self‐Assembly by Complementary Hydrogen Bonding

“…[1] To apply a greater scope of function to selfassembled cages, however, ligands with appended functional groups are required. Functionalized highly symmetric ligands are accessible, [2] but there are few simple scaffolds that are capable of both self-assembly and function, especially with regard to their reactivity once assembled. [3] If less symmetrical ligands could be employed in self-assembly, a toolbox of functionalized species for use in the creation of biomimetic self-assembled architectures would be achievable.…”