Catalytic “Click” Rotaxanes:  A Substoichiometric Metal-Template Pathway to Mechanically Interlocked Architectures

Aucagne, Vincent; Hänni, Kevin D.; Leigh, David A.; Lusby, Paul J.; Walker, D. Barney

doi:10.1021/ja056903f

Cited by 368 publications

(272 citation statements)

References 28 publications

Supporting

Mentioning

261

Contrasting

Unclassified

Order By: Relevance

“…In step A, noncovalent bonding leads to complex formation, in which the rectangles are positioned to be covalently linked under thermodynamic control in step B before being kinetically fixed in step C. Figure 2. A doll dressed in an all-in-one suit constitutes an example of a suit [5]ane.…”

mentioning

confidence: 99%

Suitanes

et al. 2006

View full text Add to dashboard Cite

The making of mechanically interlocked molecular compounds [1] has evolved from a statistical beginning [2] to the use of molecular-recognition-driven, self-assembly protocols [3] that rely upon the operation of covalent, [4] metal, [5] or noncovalent [6] templates, [7] prior to the formation of the mechanical bond(s) by either kinetically or thermodynamically controlled processes, involving either dative [8] or covalent [9] bond formation. Previously, we have speculated [10] about the existence of another class of interlocked molecule beyond the archetypal catenanes [11] and rotaxanes, [12] which are not all that dissimilar from carceplexes [13] and yet are distinguishable from them. [14] In searching for some simple term for this class of mechanically interlocked molecule (Figure 1), which consists of two separate components-a body with two or more limbs that are rigid and protrude outwards, the torso of which carries a close-fitting, all-in-one suit, such that it encompasses the torso of the body-we have come up with the term suitane, in which a number is inserted between "suit" and "ane" to indicate the number of protruding limbs. Thus, the simplest member of the series would be suit Let us consider the specific example (Scheme 1) of a linear body template [15] LBT-H 2 2+ carrying two -CH 2 -NH 2 + CH 2 -recognition sites separated from each other by a bulky midriff [16] such that the double linking up of two matching [24]crown-8 rings in the shape of (CHO) 2 -DP24C8 units [17] can be achieved reversibly by forming four imine bonds with a diaminobenzene spacer, such as p-phenylenediamine (PPD). The virtue of employing reversible imine bond formation [18] to clothe the LBT-H 2 2+ dication with two (CHO) 2 -DP24C8 units and two PPD spacers is that errors can be corrected [19] before the final structure is fixed by

show abstract

mentioning

confidence: 99%

Suitanes

et al. 2006

View full text Add to dashboard Cite

show abstract

“…Aktivtemplatsynthese Die Aktivtemplatsynthese [55] ist eine Strategie zur Bildung mechanisch verzahnter Moleküle,i nd er Metallionen eine aktive Rolle einnehmen, indem sie die bindungsbildende Reaktion katalysieren, die das Reaktionsprodukt kovalent fixiert, während sie gleichzeitig -wie die "passiven" Te mplate -die Bausteine ausrichten. Ursprünglich wurde dieser Ansatz fürd ie Vereinfachung von Rotaxan- [75,76] und Catenansynthesen [77] vorgestellt. Das Konzept konnte auch auf die Synthese eines molekularen Kleeblattknotens [78] (Schema 6) ausgeweitet werden.…”

Section: Angewandte Chemieunclassified

Molekulare Knoten

Fielden¹,

Leigh²,

Woltering³

2017

Angewandte Chemie

Self Cite

View full text Add to dashboard Cite

Der erste synthetische Kleeblattknoten wurde in den späten 1980er Jahren hergestellt. Kompliziertere Knotentopologien wurden jedoch erst in den letzten Jahren in molekularer Form erhalten. Die Verknotung molekularer Stränge erzeugt sterische Einschränkungen und kann so wichtige physikalische und chemische Eigenschaften verleihen, unter anderem Chiralität, starkes und selektives Binden von Ionen und katalytische Aktivität. Da die Anzahl und Komplexität molekularer Knoten steigt, wird es für Chemiker immer wichtiger, die Knotennomenklatur anderer Disziplinen zu verwenden. Hier geben wir einen Überblick über die Synthesestrategien für molekulare Knoten und beschreiben die Grundlagen der Knoten‐, Zopf‐ und Tangle‐Theorie in einem für Chemiker und molekulare Strukturen angemessenen Umfang.

show abstract

“…In the case of Cu(I), renowned for its role as a catalyst in the ubiquitous copper(I)-catalysed azide-alkyne cycloaddition (CuAAC) (Rostovtsev et al 2002) 'click' reaction between alkynes and azides to form 1,2,3-triazoles, rotaxanes can be formed in more than 80 per cent yields from bipyridine-based macrocycles, azide-and alkyne-substituted half-dumbbells and sub-stoichiometric quantities of the active metal template. The Cu(I) cation holds each of the three components together while also catalysing the CuAAC reaction between the two halves of the dumbbell (Aucagne et al 2006). Alternative metal templates have been exploited to a lesser extent, but many synthetic routes involve the reversibility of dynamic coordinative and covalent bonds, with the MIM being the thermodynamic product of a multi-component self-assembly process.…”

Section: Synthetic Approaches To Mechanically Interlocked Moleculesmentioning

confidence: 99%

Mechanostereochemistry and the mechanical bond

2012

View full text Add to dashboard Cite

The chemistry of mechanically interlocked molecules (MIMs), in which two or more covalently linked components are held together by mechanical bonds, has led to the coining of the term mechanostereochemistry to describe a new field of chemistry that embraces many aspects of MIMs, including their syntheses, properties, topologies where relevant and functions where operative. During the rapid development and emergence of the field, the synthesis of MIMs has witnessed the forsaking of the early and grossly inefficient statistical approaches for template-directed protocols, aided and abetted by molecular recognition processes and the tenets of self-assembly. The resounding success of these synthetic protocols, based on templation, has facilitated the design and construction of artificial molecular switches and machines, resulting more and more in the creation of integrated functional systems. This review highlights (i) the range of template-directed synthetic methods being used currently in the preparation of MIMs; (ii) the syntheses of topologically complex knots and links in the form of stable molecular compounds; and (iii) the incorporation of bistable MIMs into many different device settings associated with surfaces, nanoparticles and solid-state materials in response to the needs of particular applications that are perceived to be fair game for mechanostereochemistry.

show abstract

Catalytic “Click” Rotaxanes: A Substoichiometric Metal-Template Pathway to Mechanically Interlocked Architectures

Cited by 368 publications

References 28 publications

Suitanes

Suitanes

Molekulare Knoten

Mechanostereochemistry and the mechanical bond

Contact Info

Product

Resources

About