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Dalton Trans. 2014 Jul 7;43(25):9438-47. doi: 10.1039/c4dt00849a.

Reversible cargo shipping between orthogonal stations of a nanoscaffold upon redox input.

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  • 1Center of Micro- and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein-Str. 2, D-57068 Siegen, Germany. schmittel@chemie.uni-siegen.de.


The sterically shielded terpyridine was prepared, both as a new ligand and as part of the four-station nanoscaffold . Mixing of terpyridine , the parent phenanthroline and the shielded phenanthroline in the presence of Zn(2+) (1 : 1 : 1 : 1) furnished quantitatively the inverse HETTAP complex [Zn()()](2+) by self-sorting, while in the presence of Cu(+) the HETPHEN complex [Cu()()](+) was preferred (89%). Due to the akin coordination preferences of Cu(2+) and Zn(2+), the above self-sorting was implemented for Cu(+)/Cu(2+) on nanoscaffold , the latter equipped with the binding motifs of (PhenAr2) and (TerpyAr2). When was reacted with Cu(+) and phenanthroline () in a 1 : 2 : 2 ratio, only the PhenAr2 stations became involved in complex formation (= (Cu)phen). In contrast, upon oxidative formation of Cu(2+), ligand was exclusively moved to the TerpyAr2 stations ((Cu)terpy). Electrochemical oxidation-reduction prompted the cargo to be shipped reversibly on a subsecond time scale between the two different stations of .

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