A high-speed network of nanoswitches for on/off control of catalysis

Abstract

NetState I of the communication-catalysis protocol is defined by a 1 : 1 mixture of the nanoswitches [Cu(1)] and 2. Upon one-electron oxidation at the ferrocenyl unit of the switch [Cu(1)], copper(i) ions are released that after translocation toggle nanoswitch 2 → [Cu(2)] (NetState II) within 4 min. NetState I was fully reset within 1 min by reduction of 1+ → 1. Running this redox-triggered switching protocol in the presence of 4-nitrobenzaldehyde, diethyl malonate and piperidine (catalyst) allows toggling of a catalyzed Knoevenagel addition from ON to OFF and back to ON.

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

“…Indeed, in NetState I, the liberated catalyst 49 catalyzes the Knoevenagel addition between aldehyde 50 and diethylmalonate (51) generating product 52 in 26% yield in the first ON cycle, but only 20% in the second ON cycle. From various mechanistic investigations the conclusion was drawn that the oxidative conditions cause partial decomposition of the catalyst and thus reduce the yield in the second ON state [67].…”

“…Redox-triggered double-NetState nine-component catalytic machinery. TBA = tris(4-bromophenyl)aminium hexachloroantimonate; dmfc = decamethylferrocene[67].…”

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

“…Another use of double self-sorting has been demonstrated in examples allowing ON/OFF switching of catalysis. [46,47] Here the interdependent self-sorting, which can be regarded as a minuscule cybernetic network, comprises the two nanoswitches 31 & 32, the organocatalyst 24 and metal ions (Scheme 4). [44] The two networked states (NetStates) represent the different outcome of two self-sorting events.…”

“…Reversible double self‐sorting: two‐state machinery . Another use of double self‐sorting has been demonstrated in examples allowing ON/OFF switching of catalysis ,. Here the interdependent self‐sorting, which can be regarded as a minuscule cybernetic network, comprises the two nanoswitches 31 & 32 , the organocatalyst 24 and metal ions (Scheme ) .…”

Selective and reversible interconversion of nanosliders commanded by remote control via metal-ion signaling

“…The first examples of networked ensembles allowing ON/OFF switchable catalysis have surfaced recently. [21][22][23][24] In their key step, a nanoswitch transmitted a defined chemical signal to a functional device (e.g., nanoswitch, nanorotor, or fluorescent receptor) in response to a trigger input. Herein, we demonstrate how a remote control commands the transformation of one nanodevice into another one using the sequential translocation of more than one chemical signal.…”