A new molecular switch: redox-driven translocation mechanism of the copper cationElectronic supplementary information (ESI) available: Fig. S1: cyclic voltammetry of CuIILN2O2 in DMSO. See http://www.rsc.org/suppdata/cc/b2/b204145f/

Abstract

We report the synthesis of a novel molecular switch based on a double-stranded ditopic ligand which operates through the Cu II /Cu I couple; the mononuclear cuprous and cupric complexes were characterised by absorption spectrophotometry; reversible motion of the copper ion between the two binding sites is driven by an auxiliary oxidation and reduction reaction; the rate-limiting steps of this translocation process were determined as well as the corresponding kinetic parameters.

Route to Cluster Helicates

“…Helicates are being used in the construction of novel materials, devices, and machines with programmed properties and functions, such as luminescence, [7] DNA binding, [8] chirality, [9] magnetic exchange, [3,10] anion binding, [11] metalion translocation, [12] or electrochemical structural rearrangement. [13] However, all these possible applications could undergo remarkable development if the extremely important biological, physical, and chemical properties of cluster compounds were considered.…”

Transition metal-based chiroptical switches for nanoscale electronics and sensors

“…Variation of the structure resulted in significantly different translocation rates. Although outside the scope of this article, a related, achiral Cu(I/II)-based system was reported in collaboration with the Albrecht-Gary laboratory that included a detailed mechanistic analysis [60]. In a recent review of translocation systems [15], it was noted that metal translocation rates vary from hours to hundreds of milliseconds, depending on the ligand and metal used.…”

Redox‐Driven Intramolecular Anion Translocation between a Metal Centre and a Hydrogen‐Bond‐Donating Compartment

“…[3] A further type of controlled motion concerns the translocation of an ionic particle between two non-equivalent compartments of a molecular system. [4] Most examples involve the externally driven translocation of transition-metal ions and are based on two distinct protocols: 1) the metal exists in two oxidation states of comparable stability, and oxidation-reduction processes cause its transfer between two compartments of definitely different coordinating tendencies; [5][6][7][8][9][10][11][12] and 2) the coordinating properties of only one compartment towards a given metal ion are altered through an acid-base process, so that consecutive addition of H + and OH À ions induces a reversible intramolecular metal displacement. [13][14][15][16][17][18] On the other hand, examples of anion translocation are rare and all refer to the redox-driven transfer of an anion between two metal centres within a hetero-dinuclear complex.…”