Flip a switch: nanoswitch uses chemical inputs to turn an organocatalytic Knoevenagel reaction on and off (see scheme: R=reactant, P=product). To stop catalysis the input (pink green) wraps around inhibitory segment of effect release or unlocking switch. The process can run reversibly over three cycles without loss activity.

The reversible photoisomerization of azobenzene has been utilized to construct a plethora systems in which optical, electronic, catalytic, and other properties can be controlled by light. However, owing azobenzene's hydrophobic nature, most these examples have realized only organic solvents, operating water are relatively scarce. Here, we show that coadsorbing the inherently azobenzenes with water-solubilizing ligands on same nanoparticulate platforms, it is possible render them essentially...

Abstract Reversible switching between two states of the triangular nanoswitch [Cu( 1 )] + was accomplished by alternate addition 2‐ferrocenyl‐1,10‐phenanthroline ( 2 ) and copper(I) ions. The regulate binding release distinct catalysts, piperidine , in a fully interference‐free manner allow alternating on/off orthogonal catalytic processes. In state I, is released from catalyzes Knoevenagel 4‐nitrobenzaldehyde diethyl malonate (ON‐1 OFF‐2), while II click reaction 4‐nitrophenylacetylene...

The nanoswitches 1 and 2 are interdependently linked in so-called network states (NetStates). In NetState I, defined by presence of [Cu(1)]+ 2, the organocatalyst N-methylpyrrolidine catalyzes a conjugate addition. Addition iron(II) ions as an external chemical trigger to I discharges Cu+ from [Cu(1)]+. liberated copper(I) ion acts second messenger changes toggling state at nanoswitch 2. resulting [Cu(2)]+ captures catalytically active species solution addition is turned OFF. Removal...

Abstract The interplay of biological machines depends critically on the bidirectionality chemical information exchange. implementation such a communication procedure for abiological systems is achieved using two nanoswitches that both operate as transmitters and receivers by transfering copper ions in oxidation states +I +II. Even at micromolar concentrations, directions remarkably fast, occurring t 1/2 =2–3 min. Metal ion translocation triggers 20 Å relocation toggle nanoswitches, entailing...

The two states of a new nanomechanical switch were quantitatively and reversibly populated in several subsequent switching cycles using either Cu+ or cyclam as chemical inputs. State II was demonstrated to cis–trans isomerise diazastilbene upon irradiation selectively the presence stilbene, even operate photocatalyst.

Abstract The nanomechanical switch 1 with its three orthogonal binding motifs—the zinc(II) porphyrin, azaterpyridine, and shielded phenanthroline station—is quantitatively reversibly toggled back forth between four different switching states by means of addition removal appropriate metal‐ion inputs. Two the stages are able to initiate catalytic transformations (ON1, ON2), while two others shut down any reaction (OFF1, OFF2). Thus, in a cyclic four‐state process sequential transformation A +...

Arylazopyrazoles represent a new family of molecular photoswitches characterized by near-quantitative conversion between two states and long thermal half-lives the metastable state. Here, we investigated behavior model arylazopyrazole in presence self-assembled cage based on Pd–imidazole coordination. Owing to its high water solubility, can solubilize E isomer arylazopyrazole, which, itself, is not soluble water. NMR spectroscopy X-ray crystallography have independently demonstrated that...

Circularly polarized excimer emission is highly sought‐after due to its potential in advanced optoelectronic and sensing applications. However, achieving precise control over this phenomenon remains a significant challenge. To address challenge, we have designed system with which circularly could be controlled via conformation locking aggregation. The structural conformations were extensively examined using circular dichroism spectroscopy, X‐ray crystallography, 1H NMR molecular modelling....

Controlling synchronized motion and transmission of molecular to a remotely located guest is not trivial. Here, we demonstrate light-triggered, scissor-like conformational change in plier reversibly alter the conformation helical chirality noncovalently bound rotor guest. The comprises three building blocks: an azobenzene unit that controls open-close upon light-activated isomerization from E Z, BINOL serves as both hinge chiral inducer two pyridine moieties can form complex with...

A hydrogen-bonding interface between helical aromatic oligoamide foldamers has been designed to promote the folding of a helix-turn-helix motif with head-to-tail arrangement two helices opposite handedness. This design complements an earlier head-to-head identical handedness interface. The motifs were shown have comparable stability and combined in unimolecular tetra-helix fold constituting largest abiotic tertiary structure date.

The first true abiotic tertiary folded structures, i.e. at the exclusion of any aliphatic amino acid, have recently been introduced under form aromatic oligoamide helix-turn-helix foldamers stabilized by hydrogen bonds in organic solvents. We present an investigation interplay secondary and folding some cooperative effects these systems. A solid phase synthesis approach to preparation sequences was developed facilitate systematic variation. Flexible pyridine-based units were various...

A potential-controlled two-step bidirectional communication protocol between the nanoswitches [Cu(1)]+, 2 and 3 is set up, in which ligand followed by metal-ion oxidation drives two subsequent metal ion translocations (self-sorting) changing switching state at each switch. The reset to its starting point a two-electron reduction.

A triangular framework with a terpyridine and shielded phenanthroline at its termini constitutes an open/close nanoswitch that is toggled by chemical inputs. In the presence of copper(I) ions, open (OPEN-I) firmly closes to catalytically inactive heteroleptic [Cu(phen)(terpy)](+) complex (CLOSE). Reversible switching between CLOSE OPEN-I states was demonstrated successive addition removal Cu(+). contrast, after iron(II) ions state bishomoleptic dimeric [Fe(terpy)2](2+) formed placed in...

Structural characterization in on-surface synthesis is primarily carried out by Scanning Probe Microscopy (SPM) which provides high lateral resolution. Yet, important fresh perspectives on surface interactions and molecular conformations are gained from adsorption heights that remain largely inaccessible to SPM, but can be precisely measured with both elemental chemical sensitivity Normal-Incidence X-ray Standing Wave (NIXSW) analysis. Here, we study the evolution of post-synthetic...

Ein Nanoschalter nutzt chemische Eingaben, um eine organokatalytische Knoevenagel-Reaktion auszulösen oder zu sperren (siehe Schema: R=Reaktant, P=Produkt). Die Katalyse wird verhindert, indem die chemischen Eingaben (rosa und grün) den inhibitorischen Teil des Nanoschalters umschließen, was einer offenen Schalterstruktur führt. Der Prozess durchläuft drei Zyklen ohne Aktivitätseinbuße. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such...

Abstract Das reversible Umschalten zwischen zwei Zuständen des dreieckigen Nanoschalters [Cu( 1 )] + wurde durch wechselweise Zugabe von 2‐Ferrocenyl‐1,10‐phenanthrolin ( 2 ) und Kupfer(I)‐Ionen veranlasst. Die Schaltzustände regulieren die Bindung Freisetzung zweier unterschiedlicher Katalysatoren, Piperidin , in vollständig interferenzfreier Weise ermöglichen das abwechselnde Ein/Aus‐Schalten orthogonalen Katalyseprozessen. Im Schaltzustand I wird vom Nanoschalter freigesetzt katalysiert...

The silver(I) catch–release system composed of nanoswitch 1 and the anthracene-appended crown ether 2 is infallibly driven by chemical triggers ion transfer. Any state translocation self-reported a ratiometric emission signature at 472 554 nm. In self-sorted networked I, ions are tightly shielded inside [Ag(1)]+ ("catch") so that their catalytic activity zero while nm maximum. Addition zinc(II) releases from generates catalytically active fluorescent complex [Ag(2)]+. this II ("release")...

Abstract Das Zusammenspiel zwischen biologischen Systemen hängt entscheidend von der Bidirektionalität des chemischen Informationsaustauschs ab. Die Implementierung eines derartigen Kommunikationsprotokolls für abiologische Systeme gelingt unter Nutzung zwei Nanoschaltern, die beide Übertragung Kupferionen in den Oxidationsstufen +I und +II jeweils als Empfänger Sender eingesetzt werden können. Selbst bei mikromolaren Konzentrationen verläuft Kommunikation Richtungen mit t 1/2 =2–3 min...