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

• Published in: Dalton transactions : an international journal of inorganic chemistry 2014-07, Vol.43 (25), p.9438-9447
• Main Authors: Samanta, Soumen K, Rana, Anup, Schmittel, Michael
• Format: Article
• Language: English
• Subjects: Binding; Cargo ships; Complex formation; Coordination Complexes - chemistry; Copper - chemistry; Electrochemistry; Inverse; Ligands; Models, Molecular; Nanostructure; Nanostructures - chemistry; Oxidation-Reduction; Phenanthrolines - chemistry; Pyridines - chemistry; Stations; Zinc - chemistry
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c4dt00849a

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 .