A Simple General Ligand System for Assembling Octahedral Metal–Rotaxane Complexes

Hogg, Louise; Leigh, David A.; Lusby, Paul J.; Morelli, Alessandra; Parsons, Simon; Wong, Jenny K. Y.

doi:10.1002/ange.200353186

Cited by 51 publications

(7 citation statements)

References 45 publications

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“…This "3+3" approach required modification to realize the analogous rotaxanes, as using imine ligand 51 in conjunction with a similar tridentate thread would lead to formation of undesired thread-thread and pre-catenate complexes. [49] Instead bisamine macrocycle (57) was coordinated to various divalent metal ions and directed imine-bond formation between 'stopper' aniline 58 and 2,6-diformylpyridine (55) through the cavity of the macrocycle to generate rotaxanes (59) (Scheme 1.22). The success of this strategy lay in the use of imine bond formation, allowing assembly and disassembly of the many possible structures in order to find the most thermodynamically favored product.…”

Section: "3+3" Octahedral Strategymentioning

confidence: 99%

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Active metal template synthesis of rotaxanes, catenanes and molecular shuttles

et al. 2009

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Active metal template synthesis is a powerful new strategy for the construction of rotaxanes, catenanes and other mechanically interlocked molecular structures. The key feature is that the metal plays a dual role during the assembly of the interlocked architecture, acting as both a template for entwining or threading the components and as a catalyst for capturing the interlocked final product by covalent bond formation. Unlike traditional "passive" metal template methods to rotaxanes and catenanes, permanent recognition motifs are not required on each of the components to be interlocked (i.e., the assembly can be traceless) and the template can often be used in sub-stoichiometric quantities. Since its inception in 2006, a rapidly growing number of different metal-catalysed reactions have proven suitable for the active metal template synthesis of both rotaxanes and catenanes, including the copper(i)-catalysed terminal alkyne-azide cycloaddition (the CuAAC "click" reaction), palladium- and copper-catalysed alkyne homocouplings and heterocouplings, and palladium-catalysed oxidative Heck couplings and Michael additions. In addition to simple rotaxanes and catenanes, the synthetic strategy has been used to construct switchable molecular shuttles with weak intercomponent interactions (a requirement for fast shuttling) and to provide insight into the mechanisms of transition metal-catalysed reactions. In this tutorial review we highlight the utility and potential of the early examples of the active metal template strategy in mechanically interlocked molecule synthesis.

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Section: "3+3" Octahedral Strategymentioning

confidence: 99%

“…Octahedral amine/imine-based[2]rotaxanes 59 formed through imine bond formation. Shown on the right is the crystal structure of rotaxane 59-Cd(II) [49]. …”

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Active metal template synthesis of rotaxanes, catenanes and molecular shuttles

et al. 2009

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“…[166] Ein ähnlicher oktaedrischer "4+2"-Donorligandensatz kam auch bei der Templatsynthese von Rotaxanen zum Einsatz (Schema 30). [167] [163] Für eine ähnliche [2]Catenatsynthese siehe Schema 7. [76] Schema 29.…”

Section: -Cu Iunclassified

Strategien und Taktiken für die metallgesteuerte Synthese von Rotaxanen, Knoten, Catenanen und Verschlingungen höherer Ordnung

et al. 2011

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Mehr als ein Vierteljahrhundert nach der ersten Metalltemplatsynthese eines [2]Catenans in Straßburg existiert nun eine Fülle an Strategien zum Aufbau mechanisch verbundener und verflochtener Strukturen auf molekularer Ebene. Catenane, Rotaxane, Knoten und Borromäische Ringe sind alle erfolgreich über Methoden zugänglich, in denen Metallionen eine Schlüsselrolle spielen. Ursprünglich wurden Metallionen ausschließlich aufgrund ihrer Koordinationschemie verwendet, indem sie entweder die einzelnen Bausteine auf eine Weise anordneten, die durch anschließende Reaktionen die Erzeugung der verschlungenen Produkte ermöglichte, oder indem sie selbst als wesentlicher Bestandteil der Ringe oder als “Stopper” dienten. Vor kurzem wurde die Rolle des Metalls auch auf die Katalyse ausgedehnt: Die Metallionen ordnen die Bausteine nicht nur zu einer verflochtenen oder eingefädelten Struktur an, sondern fördern auch aktiv die Strukturbildung durch kovalenten Einfangen. Dieser Aufsatz fasst die Strategien zur Bildung mechanisch verbundener Molekülstrukturen mit Metallionen zusammen und diskutiert die Taktiken, die zum Aufbau von Überkreuzungen, zur Maximierung der Ausbeuten verschlungener und nichtverschlungener Produkte und zur Bildung eingefädelter oder verflochtener Intermediate durch kovalenten Einfang zur Verfügung stehen.

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“…Two control receptors, R2′ and R3′ having the same linkers but lacking the NDI units, were also synthesized to decipher the cation-induced changes and the anion recognition capability of R2 and R3 . The tridentate linker used in R3 and R3′ is known to chelate transition metal ions and form interlocked 2:1 host–guest complexes. , …”

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“…The tridentate linker used in R3 and R3′ is known to chelate transition metal ions and form interlocked 2:1 host−guest complexes. 32,33 34 No such complex was formed with the corresponding Bu 4 N + salts. These results not only revealed 2:1 stoichiometry of R3 and M II in the complexes, but also suggested that M II coordination by the tridentate linker enabled R3 to capture a guest anion at a different location.…”

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Cation-Assisted Reversible Folding and Anion Binding by a Naphthalenediimide-Based Ditopic Ion-Pair Receptor

et al. 2018

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A novel heteroditopic ion-pair receptor was synthesized by tethering two π-acidic naphthalenediimide units with a tridentate bisimine linker. Upon chelating a Zn or Cd ion with the linker, it adopts a U-conformation allowing the parallel NDI arms to sandwich charge-diffuse anions, and two such folded receptor molecules interlock with each other forming an [R3·M·R3·X] ion-pair complex. Extraction of the guest cation with a tetraazacrown ether returns the receptor to its original unfolded form.

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A Simple General Ligand System for Assembling Octahedral Metal–Rotaxane Complexes

Abstract: Ummantelt: Durch einfaches Rühren einer Mischung aus fünf Komponenten bei Raumtemperatur lässt sich eine Vielzahl oktaedrisch koordinierter [2]Metallorotaxane thermodynamisch kontrolliert herstellen (siehe Bild).

Cited by 51 publications

References 45 publications

Active metal template synthesis of rotaxanes, catenanes and molecular shuttles

Active metal template synthesis of rotaxanes, catenanes and molecular shuttles

Strategien und Taktiken für die metallgesteuerte Synthese von Rotaxanen, Knoten, Catenanen und Verschlingungen höherer Ordnung

Cation-Assisted Reversible Folding and Anion Binding by a Naphthalenediimide-Based Ditopic Ion-Pair Receptor

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