Issue 12, 2011

Control of metal-directed self-assembly by metal–amine interactions

Abstract

The complexation of a tweezers ligand with zinc perchlorate in the absence and presence of amines in methanol solution was explored. L2Zn2(ClO4)4 was a thermodynamic product of the reaction in the absence of an amine. The complex was shown to interact with aliphatic amines resulting in the formation of a Zn–N(amine) bond. If metal–ligand complexation was carried out in the presence of an amine the formation of a trinuclear zinc complex L3Zn36+ was observed. Moreover the transformation of complex L2Zn24+ to L3Zn36+ occurred, when the former was subjected to an amine in the amount, which is sufficient to coordinate more than one amino group on each zinc atom. Complexes ligand-zinc-amine were shown to be kinetically stable, and the method of their preparation was crucial to the purity of the final complexes. L3Zn36+ was favored under kinetic control: reagent concentration 10−5M, slow addition of zinc perchlorate to the mixture of an amine and the ligand. Under thermodynamic control (fast mixing of reagents, concentration 10−2–10−3 M) formation of a mixture of complexes was observed. All pure complexes and their mixtures were characterized using UV-Vis, ROESY, PFGSE NMR and ESI-MS techniques. On the basis of DFT calculations the mechanism of influence of an amine on self-assembly was suggested.

Graphical abstract: Control of metal-directed self-assembly by metal–amine interactions

Supplementary files

Article information

Article type
Paper
Submitted
18 Aug 2010
Accepted
06 Dec 2010
First published
07 Feb 2011

Dalton Trans., 2011,40, 2778-2786

Control of metal-directed self-assembly by metal–amine interactions

E. A. Katayev and M. B. Schmid, Dalton Trans., 2011, 40, 2778 DOI: 10.1039/C0DT01056A

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