Was können wir von der Natur über die Reaktivität koordinierter Phenoxylradikale lernen? – Eine bioanorganische Glanzleistung

Materialien sind die ersten templatgesteuerten Nanostrukturen mit Periodizitäten im Bereich der Wellenlänge sichtbaren Lichts, daher sind sie vielversprechend für photonische Kristalle. [12] Wissenschaftler haben diese phantasievolle, einfache und erfolgreiche Methode zur Strukturierung von Materielien etabliert, jetzt ist es Zeit, an die Anwendungen zu denken und das vielversprechende und vielfach versprochene Prinzip der ¹porösen Nanostrukturª auf den Prüfstand zu schicken. Die Autorin freut sich darauf, auch dies bald in der hochrangigen Fachliteratur dokumentiert zu finden.

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Biomimetic Copper(I)-CO Complexes: A Structural and Dynamic Study of a Calix[6]arene-Based Supramolecular System

Rondelez

Sénèque

Rager

et al. 2000

Chem. Eur. J.

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Four novel calix[6]arene-based cuprous complexes are described. They present a biomimetic tris(imidazole) coordination core associated with a hydrophobic cavity that wraps the apical binding site. Each differs from the other by the methyl or ethyl substituents present on the phenoxyl groups (OR1) and on the imidazole arms (NR2) of the calix[6]arene structure. In solution, stable CO complexes were obtained. We have investigated their geometrical and dynamic properties with respect to the steric demand. IR and NMR studies revealed that, in solution, these complexes adopted two distinct conformations. The preferred conformation was dictated only by the size of the OR1 group. When R1 was an ethyl group, the complex preferentially adopted a flattened C3-symmetrical structure. The corresponding helical enantiomers were in conformational equilibrium, which, however, was slow on the 1H NMR time scale at -80 degrees C. When R1 was a methyl group, the low-temperature NMR spectra revealed the partial inclusion of one tBu group. The complex wobbled between three dissymmetric but equivalent conformations. Hence, small differences in the steric demand of the calixarene's skeleton changed the geometry and dynamics of the system. Indeed, this supramolecular control was promoted by the strong conformational coupling between the metal center and the host structure. Interestingly, this was not only the result of a covalent preorganization, but also stemmed from weak interactions within the hydrophobic pocket. The vibrational spectra of the bound CO were revealed to be a sensitive gauge of this supramolecular behavior, similar to copper proteins in which allosteric effects are common.

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Was können wir von der Natur über die Reaktivität koordinierter Phenoxylradikale lernen? – Eine bioanorganische Glanzleistung

Cited by 4 publications

References 31 publications

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Biomimetic Copper(I)-CO Complexes: A Structural and Dynamic Study of a Calix[6]arene-Based Supramolecular System

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