The magic effect of endocyclic but non-sterically hindering biisoquinoline chelates: From fast-moving molecular shuttles to [3]rotaxanes

Durola, Fabien; Sauvage, Jean‐Pierre; Wenger, Oliver S.

doi:10.1016/j.ccr.2009.09.034

Cited by 52 publications

(15 citation statements)

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“…A thermodynamic template works essentially the same, except that the intermediates are in equilibrium, which allows for the selection of the most stable one and the product thereof. The earliest metal templates that were used for making catenanes and rotaxanes were based on the Cu(dpp) 2 + complex fragment in which the Cu(I) cation in tetrahedral geometry intertwines two dpp (2,9-diphenyl-1,10-phenanthroline) chelates orthogonally to each other and this was followed by many other Cu(I) bis-diimine complex systems [10]. Other coordination geometries were demonstrated to work equally well (Figure 2), providing that the adequate metal/ligand combination is chosen, for example linear (two-coordinate) Au(I)/pyridyl (py) [11] and octahedral (six-coordinate) Ru(II)/2,2′;6′, 2″-terpyridyl (terpy) [12].…”

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Transition metal-templated synthesis of catenanes and rotaxanes

Chambron

Sauvage

2011

Sci. China Chem.

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Catenanes are molecules made of two or more interlocked rings, and rotaxanes are composed of rings threaded onto axles that look like dumbbells because they are terminated by stoppers large enough to prevent unthreading ( Figure 1) [1]. [n]Catenanes are constituted by n interlocked rings, whereas [n]rotaxanes are made of n-m rings and m dumbbell components. Both constitute the prototypical molecular objects featuring the so-called "mechanical bond". Whereas the first syntheses of catenanes and rotaxanes date back to the late sixties [2], the real burst of these exotic-at-that-time classes of compounds really started a decade later, after the very first template methods (metal coordination [3], and - donor-acceptor interactions [4]) were discovered and developed [5,6]. Since then catenanes and rotaxanes, from the status of molecular curiosities (in terms of topology and synthetic access), attained the rank of useful synthetic molecules that could be endowed with functions. Indeed, the last two decades have seen the development of molecular machines that rely heavily on catenanes and rotaxanes, taking advantage of the mechanical bonds for the generation and observation of net molecular motions [7,8]. This contribution will account for the metal template technology, as among all the methods developed for making interlocked molecules, it is certainly the one that proved itself to be the most versatile and productive. Figure 1 The simplest [2]catenane and [2]rotaxane, made of two interlocked components.The exceptional power of metal templates, and especially transition metal templates, stems from their richness and variety in terms of coordination geometries, oxidation states, bond strength and lability, and reactivity. Metal templates were early recognized as being either kinetic and/or thermodynamic, depending on the property used [9]. A kinetic template preorganizes the reactants in order to drive the formation of a geometrically-or topologically-selective reaction, that is for instance a macrocycle vs. a polymer, or a catenane vs a macrocycle. A thermodynamic template works essentially the same, except that the intermediates are in equilibrium, which allows for the selection of the most stable one and the product thereof. The earliest metal templates that were used for making catenanes and rotaxanes were based on the Cu(dpp) 2 + complex fragment in which the Cu(I) cation in tetrahedral geometry intertwines two dpp (2,9-diphenyl-1,10-phenanthroline) chelates orthogonally to each other and this was followed by many other Cu(I) bis-diimine complex systems [10]. Other coordination geometries were demonstrated to work equally well (Figure 2), providing that the adequate metal/ligand combination is chosen, for example linear (two-coordinate) Au(I)/pyridyl (py) [11] and octahedral (six-coordinate) Ru(II)/2,2′;6′, 2″-terpyridyl (terpy) [12]. The use of less straightforward four-coordinate square planar (sp) Pd(II), and five-coordinate square-based pyramidal (sqp) and trigonal bipyramidal (tbp) Zn(II) and Cu(II) involved...

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Transition metal-templated synthesis of catenanes and rotaxanes

Chambron

Sauvage

2011

Sci. China Chem.

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“…Another interesting possibility is to trap a cyclodextrin molecule between linked bulky complexes, leading to the formation of rotaxanes [24].…”

Section: Introductionmentioning

confidence: 99%

Triangular ruthenium acetate clusters containing the bis(pyridyl)propane ligand and their inclusion chemistry with β-cyclodextrin

Nikolaou

Toma

Souza

et al. 2011

Transition Met Chem

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The triruthenium carboxylate cluster [Ru 3 O-(OAc) 6 (py) 2 (bpp)] ? (OAc = acetate) containing the bridging 1,3-bis(4-pyridyl)propane (bpp) ligand, and its dimeric species [{Ru 3 O(OAc) 6 (py 2 )} 2 (l-bpp)] 2? were synthesized in order to investigate their inclusion compounds with b-cyclodextrin (b-CD). Characterization of the complexes was carried out based on spectroscopic, electrochemical and spectroelectrochemical techniques, while the formation of inclusion complexes was evaluated using 1 H NMR/ NOESY spectroscopy. Since bpp is a flexible ligand, a DFT study was carried out in order to characterize its conformational isomers and their possible role in the host-guest chemistry with b-CD. Instead of observing the formation of inclusion compounds with different stoichiometries, we observed the formation of 1:1 bpp/b-CD compounds in which the bpp ligand assumes different conformations. The assembly of polymetallic rotaxane species was successfully demonstrated by monitoring the 1 H NMR spectra of the monomeric cluster species in the presence of aquapentacyanoferrate(II) ions and b-CD.

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“…Sauvage’s group could, for instance, increase the kinetics of a shuttle based on a [3]rotaxane by four orders of magnitude by replacing the sterically hindered phenanthroline macrocycle by a non‐sterically hindering biisoquinoline chelate (Figure 11 B). 49…”

Section: Redox‐driven Molecular Machines In Solutionmentioning

confidence: 99%

“…B) Two different macrocycles containing a phenanthroline (left) and a biisoquinoline (right) chelate 48. 49…”

Section: Redox‐driven Molecular Machines In Solutionmentioning

confidence: 99%

Size‐Induced Chiral Discrimination Switching by (S)‐(−)‐2(α‐Hydroxyethyl)Benzimidazole‐Derived Azacrowns

et al. 2014

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(S)‐(−)‐2‐(α‐Hydroxyethyl)benzimidazole (1)‐derived diastereomeric monoaza‐[18]crown‐6 compounds 5 and 6 were synthesised with an additional chiral centre bearing a phenyl ring. The aim was to achieve enhanced enantioselective discrimination, compared with monoaza‐[15]crown‐5 (7). Surprisingly, reversal of enantioselective binding for chiral guest enantiomers between the two differently sized [15]crown‐5 and [18]crown‐6 azacrowns were discovered; all three were prepared from the same parent compound, 1. To complete the observations, another [18]crown‐6‐sized azacrown (10) without an additional chiral centre was synthesised from 1 and screened for its enantioselective binding abilities towards the chiral guest enantiomers investigated; these results corroborated the observations. Single‐crystal XRD analysis and molecular docking studies revealed that changes to the conformational aspects of [18]crown‐6 and [15]crown‐5 azacrowns were the major contributing factors to this peculiar behaviour.

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The magic effect of endocyclic but non-sterically hindering biisoquinoline chelates: From fast-moving molecular shuttles to [3]rotaxanes

Cited by 52 publications

References 88 publications

Transition metal-templated synthesis of catenanes and rotaxanes

Transition metal-templated synthesis of catenanes and rotaxanes

Triangular ruthenium acetate clusters containing the bis(pyridyl)propane ligand and their inclusion chemistry with β-cyclodextrin

Size‐Induced Chiral Discrimination Switching by (S)‐(−)‐2(α‐Hydroxyethyl)Benzimidazole‐Derived Azacrowns

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