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

Schmittel, Michael

doi:10.1002/ijch.201800124

Cited by 26 publications

(21 citation statements)

References 77 publications

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“…While fluxional molecules involving bond cleavage/formation have a long‐standing history, related dynamics within multiple degenerate structures in supramolecular multicomponent devices is scarce . Herein, for the first time, multicomponent rotors are equipped with fluxional axles allowing them to undergo domino rotation. Such domino rotors are characterized by a unique feature: the rotator arm of the first rotor subunit intra(supra)molecularly interconverts into the axle of the second rotor subunit.…”

Section: Methodsmentioning

confidence: 99%

Double Rotors with Fluxional Axles: Domino Rotation and Azide–Alkyne Huisgen Cycloaddition Catalysis

Goswami

Schmittel

2020

Angew Chem Int Ed

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The simple preparation of the multicomponent devices [Cu4(A)2]4+ and [Cu2(A)(B)]2+, both rotors with fluxional axles undergoing domino rotation, highlights the potential of self‐sorting. The concept of domino rotation requires the interconversion of axle and rotator, allowing the spatiotemporal decoupling of two degenerate exchange processes in [Cu4(A)2]4+ occurring at 142 kHz. Addition of two equiv of B to rotor [Cu4(A)2]4+ afforded the heteromeric two‐axle rotor [Cu2(A)(B)]2+ with two distinct exchange processes (64.0 kHz and 0.55 Hz). The motion requiring a pyridine→zinc porphyrin bond cleavage is 1.2×105 times faster than that operating via a terpyridine→[Cu(phenAr2)]+ rupture. Finally, both rotors are catalysts due to their copper(I) content. The fast domino rotor (142 kHz) was shown to suppress product inhibition in the catalysis of the azide–alkyne Huisgen cycloaddition.

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Section: Methodsmentioning

confidence: 99%

Double Rotors with Fluxional Axles: Domino Rotation and Azide–Alkyne Huisgen Cycloaddition Catalysis

Goswami

Schmittel

2020

Angew Chem Int Ed

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“…The chemical communication protocol demonstrates its potential for sophisticated information transfer [20] within a mixture and extends the seminal work by Lehn on molecular actuator & engine type of devices "fueled" by ion flow. [7a,b] Both the synthesis and regulation of mechanical motion through naked-eye colorimetric and luminescence changes allow one to follow the finely-tuned operation within network.…”

Section: Synthesis Of Rotaxanementioning

confidence: 73%

Remote Control of the Synthesis of a [2]Rotaxane and its Shuttling via Metal‐Ion Translocation

et al. 2019

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This paper is dedicated to Prof. Jean-Marie Lehn on the occasion of his 80th birthday with deep gratitude for his inspiring and groundbreaking work.Remote control in an eight-component network commanded both the synthesis and shuttling of a [2]rotaxane via metal-ion translocation, the latter being easily monitored by distinct colorimetric and fluorimetric signals. Addition of zinc(II) ions to the red colored copper-ion relay station rapidly liberated copper(I) ions and afforded the corresponding zinc complex that was visualized by a bright sky blue fluorescence at 460 nm. In a mixture of all eight components of the network, the liberated copper(I) ions were translocated to a macrocycle that catalyzed formation of a rotaxane by a double-click reaction of acetylenic and diazide compounds. The shuttling frequency in the copper-loaded [2]rotaxane was determined to k 298 = 30 kHz (ΔH � = 62.3 � 0.6 kJ mol À 1 , ΔS � = 50.1 � 5.1 J mol À 1 K À 1 , ΔG � 298 = 47.4 kJ mol À 1 ). Removal of zinc(II) ions from the mixture reversed the system back generating the metal-free rotaxane. Further alternate addition and removal of Zn 2 + reversibly controlled the shuttling mode of the rotaxane in this eight-component network where the ion translocation status was monitored by the naked eye.[a] I.

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“…Während fluktuierende Moleküle mit Bindungsspaltung/‐bildung eine lange Geschichte aufweisen, ist eine ähnliche Dynamik innerhalb multipler entarteter Strukturen in supramolekularen Mehrkomponentengeräten selten . Erstmals werden hier Mehrkomponentenrotoren mit fluktuierenden Achsen ausgestattet, die eine Domino‐Rotation ermöglichen. Solche Domino‐Rotoren zeichnen sich durch ein einzigartiges Merkmal aus: Der Rotatorarm der ersten Rotoruntereinheit wandelt sich intra(supra)molekular in die Achse der zweiten Rotoruntereinheit um.…”

Section: Methodsunclassified

Doppelrotoren mit fluktuierenden Achsen: Domino‐Rotation und Katalyse der Azid‐Alkin‐Huisgen‐Cycloaddition

Goswami

Schmittel

2020

Angewandte Chemie

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Die einfache Herstellung der Mehrkomponentengeräte [Cu4(A)2]4+ und [Cu2(A)(B)]2+, beides Rotoren mit fluktuierenden Achsen, die sich in einer Domino‐Rotation befinden, unterstreicht das Potenzial der Selbstsortierung. Das Konzept der Domino‐Rotation erfordert die Interkonversion von Achse und Rotator, was die räumlich‐zeitliche Entkopplung zweier entarteter Austauschprozesse in [Cu4(A)2]4+ ermöglicht, die mit 142 kHz auftreten. Die Addition von zwei Äquivalenten B zum Rotor [Cu4(A)2]4+ führte zum heteromeren zweiachsigen Rotor [Cu2(A)(B)]2+ mit zwei unterschiedlichen Austauschprozessen (64.0 kHz und 0.55 Hz). Die Bewegung, die eine Spaltung der Pyridin→Zinkporphyrin‐Bindung erfordert, ist 1.2×105‐mal schneller als diejenige, die über eine Spaltung der Terpyridin→[Cu(phenAr2)]+‐Bindung erfolgt. Schließlich sind beide Rotoren wegen ihres Kupfer(I)‐Anteils Katalysatoren. Es konnte gezeigt werden, dass der schnelle Domino‐Rotor (142 kHz) die Produktinhibierung bei der Katalyse der Azid‐Alkin‐Huisgen‐Cycloaddition unterdrückt.

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

Cited by 26 publications

References 77 publications

Double Rotors with Fluxional Axles: Domino Rotation and Azide–Alkyne Huisgen Cycloaddition Catalysis

Double Rotors with Fluxional Axles: Domino Rotation and Azide–Alkyne Huisgen Cycloaddition Catalysis

Remote Control of the Synthesis of a [2]Rotaxane and its Shuttling via Metal‐Ion Translocation

Doppelrotoren mit fluktuierenden Achsen: Domino‐Rotation und Katalyse der Azid‐Alkin‐Huisgen‐Cycloaddition

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