And rotaxanes

Another synthetic strategy is based on self-assembly driven by molecular recognition between complementary TT-donors and 7T-acceptors. Examples include the synthesis of catenanes and rotaxanes that can act as controUable molecular shuttles (6,236). The TT-donors in the shuttles are located in the dumb-beU shaped component of the rotaxane and the 7T-acceptors in the macrocycHc component, or vice versa. The shuttles may be switched by chemical, electrochemical, or photochemical means. 

Catenanes and rotaxanes including macroheterocyclic fragments 99T5265. 

Nonionic template synthesis of amide-linked catenanes and rotaxanes with macroheterocyclic fragments 97AG(E)930. 

This molecule has no chiral carbons, nor does it have a rigid shape, but it too has neither a plane nor an alternating axis of symmetry. Compound 32 has been synthesized and has, in fact, been shown to be chiral. Rings containing 50 or more members should be able to exist as knots (33, and see 37 on p. 114 in Chapter 3). Such a knot would be nonsuperimposable on its mirror image. Calixarenes, ° crown ethers, catenanes, and rotaxanes (see p. 113) can also be chiral if suitably substituted. For example, A and B are nonsuperimposable mirror images. 

Other supramolecular structures such as catenanes and rotaxanes can be formed using zinc as a template ion for example, a benzylic imine catenate formed by Leigh et a/.288 The reversible five-component assembly of a [2]catenane from a chiral metallomacrocycle and a dinaphtho-crown ether has been achieved. Zinc is used as the metal component and drives assembly via the coordination to a bipyridyl unit 7r interactions between the aromatic components are also... 

Sauvage, J.-P. Dietrich-Buchecker, G. Molecular Catenanes and Rotaxanes and Knots-, Wiley-VCH Weinheim, 1999. 

R. Jager, F. Vogtle, A New Synthetic Strategy towards Molecules with Mechanical Bonds Nonionic Template Synthesis of Amide-Linked Catenanes and Rotaxanes , Angew. Chem Int. Ed. Engl. 1997,36,930-944. 

As will be discussed later, ammonium salts have also been used as hydrogen bond-donor templates to favour the formation of macrocycles (yielding pseu-dorotaxanes and rotaxanes). 

The strong hydrogen bonding interactions observed between the oxygen atoms of crown ethers and the N-H groups of ammonium groups can be successfully employed to prepare pseudorotaxanes and rotaxanes by templated processes. This approach has been extensively utilised by Stoddart, Busch and others to obtain a wide range of interlocked species. 

Loeb has reported a series of pseudorotaxanes [84,85] and rotaxanes [86,87] where C-H- 0 hydrogen bonding interactions (together with N+- -O attractive forces) play an important contribution in templating the formation of the interlocked species. In particular, the formation of a pseudorotaxane was observed when equimolar amounts of [pyCH2CH2py]2+ and the crown ether 20 were mixed. The structural characterization of the resulting host-guest complex... 

Scheme 33 Loeb has reported the templated syntheses of a series of pseudorotaxanes and rotaxanes which is based on C-H---0 hydrogen bonding interactions as the main directing force... 

Figure 12.16 shows a schematic representation of intercomponent motions that can be obtained in pseudorotaxanes and rotaxanes. 

Table 3 Absorption and emission of squaraine and rotaxanes in THF-water (4 1) [52]...

Table 7 Spectral characteristics of squaraine 23a and rotaxane [23a C 25 D Na2][2C104] in acetonitrile [63]...

Especially, the subdivision in different hydrogen bond acceptor atom sets improves the performance of the SEN approach while a subdivision depending on the hydrogen bond donor atom showed only a minor improvement compared to the general fit of Reiher et al. Thus, the SEN approach has proven as a tool to investigate hydrogen bonds of, e.g., transition metal compounds (171,174-177), peptides (178), enzymes (179), DNA and RNA (173), molecular switches (180), ionic liquids (181,182), and rotaxanes (183). However, the SEN approach is not solely restricted to hydrogen bond detection. This approach can also be apphed to determine the covalent interaction between metal atoms (184) or phosphorus atoms (162,185). Therefore, it is suitable for different kind of interactions. 

Y. F. Ng, J. C. Meillon, T. Ryan, A. P. Dominey, A. P. Davis and J. . M. Sanders, Gel-phase MAS NMR spectroscopy of a polymer-supported pseudorotaxane and rotaxane Receptor binding to an inert polyethylene glycol spacer, Angewandte Chemie-International Edition, 2001, 40, 1757-1760. 

Catenanes and rotaxanes represent examples of interlocked architectures. A catenane consists of two interlocked rings (it is called in this case a [2]catenane),... 

Interestingly, the dumbbell component of a molecular shuttle exerts on the ring motion the same type of directional restriction as imposed by the protein track for linear biomolecular motors (an actin filament for myosin and a microtubule for kinesin and dynein).4 It should also be noted that interlocked molecular architectures are largely present in natural systems—for instance, DNA catenanes and rotaxanes... 

Several examples of catenanes and rotaxanes have been constructed and investigated on solid surfaces.1 la,d f 12 13 26 If the interlocked molecular components contain electroactive units and the surface is that of an electrode, electrochemical techniques represent a powerful tool to study the behavior of the surface-immobilized ensemble. Catenanes and rotaxanes are usually deposited on solid surfaces by employing the Langmuir-Blodgett technique27 or the self-assembled monolayer (SAM) approach.28 The molecular components can either be already interlocked prior to attachment to the surface or become so in consequence of surface immobilization in the latter setting, the solid surface plays the dual role of a stopper and an interface (electrode). In most instances, the investigated compounds are deposited on macroscopic surfaces, such as those of metal or semiconductor electrodes 26 less common is the case of systems anchored on nanocrystals.29... 

Electrochemically Driven Molecular Machines Based on Transition-metal Complexed Catenanes and Rotaxanes... 

In this chapter, we will focus on transition metal-based catenanes and rotaxanes. We will restrict ourselves to compounds that are set in motion by an electrochemical signal. Indeed, the electrochemical techniques represent privileged methods for piloting these machines since they contain electroactive transition metal centers or complexes. In addition to triggering the motions, electrochemistry allows to investigate the dynamic properties of the compounds. 

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