Novel [2]Catenane Structures Introducing Communication between Transition Metal Centers via π···π Interactions
- 1 September 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 123 (38) , 9356-9366
- https://doi.org/10.1021/ja0108537
Abstract
[2]Catenane systems containing copper(II) and nickel(II) as metal centers have been self-assembled using tetraazamacrocyclic complexes and benzo-24-crown-8 as building blocks. A variety of methods, including X-ray crystallography, ESI mass spectrometry, 13C and 1H NMR, and electrochemistry, were applied to characterize these new face-to-face bismacrocyclic systems. Weak π···π interactions introduced by interlocking transition metal complexes with benzocrown moieties were shown to increase the communication (cooperativity) of metal centers. Introduction of the benzocrown increases the stability of the mixed valence state of the macrocyclic complex, which is reflected in high values of conproportionation constants. Moreover, this effect was found to be stronger than that obtained by shortening the length of the spacer between the two tetraazamacrocyclic subunits in the parent bismacrocycles. The extent of communication is larger for the nickel catenane than for the copper one.Keywords
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