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

Abstract

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 .

Heteroleptic copper phenanthroline complexes in motion: From stand-alone devices to multi-component machinery

“…The three-component device [ [4] Cu 2 (25) 2 (38)] 2+ has been fabricated to allow for redox triggered cargo transfer from the phenanthroline to the pyridine-phenanthroline stations ( Fig. 21) [57]. Upon loading the scaffold 38 with two copper(I) ions and two ligands 25, the initial self-sorting generates the corresponding HETPHEN complexes on the phenanthroline stations of 38.…”

Dynamic Functional Molecular Systems: From Supramolecular Structures to Multi‐Component Machinery and to Molecular Cybernetics

“…Along with this transformation the originally non‐fluorescent copper(I) rectangle was transformed into the luminescent ladder [Zn 4 ( 29 ) 2 ( 30 ) 2 ] 8+ . Other examples include redox‐triggered cargo shipping and switching, as well as Hosseini's turnstiles ,…”

“…Along with this transformation the originally nonfluorescent copper(I) rectangle was transformed into the 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 luminescent ladder [Zn 4 (29) 2 (30) 2 ] 8 + . Other examples include redox-triggered cargo shipping [41] and switching [42,43] as well as Hosseini's turnstiles. [44,45] Reversible double self-sorting: two-state machinery.…”

Ferrocene Rotary Switches Featuring 2‐Pyridyl‐1,2,3‐triazole “Click” Chelates

“…The bpy arms of the diebpyFc‐rotor are forced into an anti ‐conformation due to the steric bulk of the mesityl groups and charge repulsion of the cationic Cu(I) metal ions. The reformation of the syn stacked conformation can be achieved chemically (by the addition of 1,4,8,11‐tetraazacyclotetradecane (cyclam) to extract the Cu(I) ions from the system) [25] or electrochemically (in the presence of 2,2′;6′,2“‐terpyridine (terpy)) [26] . The system was further extended into a more complicated molecular folding‐ruler system that could be triggered to extend and contract using similar conditions [21b] .…”