Charge catenanes

Figure B. Pictorial representation of the self-assembly of pseudorotaxa-nes based on (a) charge-transfer and C-H—O hydrogen-bonding interactions between 1,1 -diben-zyl-4,4 -bipyridinium dication and 1,5-dinaphtho[38] crown-10 (1/5DN38C10), and (b) hydrogen-bonding interactions between dibenzyl ammonium ion and dibenzo[24]crown-8 (DB24C8). A possible route towards the synthesis of rotaxanes and catenanes is also schematized.

Figure 4. Schematic energy level diagram for a catenane based on charge-transfer (CT) interactions and for its separated components. The wavy lines indicate nonradiative decay paths of the electronic excited states.

Fujimoto and coworkers used a self-assembled Janus [2]-pseudorotaxane406 to obtain a Janus[2]rotaxane 407 (Figure 8.2.4) [33]. A quadruply stranded alkaline earth metal containing helical catenate, a charge-neutral heterotopic homodinuclear [2]catenane, was reported by Castro et al. [34]. 

When rotaxanes and catenanes contain redox-active units, electrochemical techniques are a very powerful means of characterization. They provide a fingerprint of these systems giving fundamental information on (i) the spatial organization of the redox sites within the molecular and the supramolecular structure, (ii) the entity of the interactions between such sites, and (iii) the kinetic and thermodynamic stabilities of the reduced/oxidized and charge-separated species. 

In this chapter, for space reasons, only a few paradigmatic examples of rotaxanes and catenanes based on donor-acceptor (charge transfer (CT)) and/or hydrogen bonding interactions (systems based on metal-ligand bonding are reviewed in another... 

Figure 13.22 The circumrotation of the tetracationic cyclophane component of catenane 254+ can be controlled reversibly by adding-protonating -hexylamine that forms a charge transfer adduct with the diazapyrenium unit of the catenane.

Wozniak and coworkers described recently the first heterodinuclear bismacrocyclic transition metal complex 34 + (Fig. 14.5) that exhibits potential-driven intramolecular motion of the interlocked crown ether unit.25 26 Although the system contains transition metals, the main interaction between the various subunits, which also allowed to construct catenane 34+, is an acceptor-donor interaction of the charge transfer type. 

In a serendipitous fashion, a novel mixed valence tetranuclear copper(II)/copper(III) dithiocarbamate [2]catenane was prepared in near quantitative yield by partial chemical oxidation of a preformed dinuclear copper(II) naphthyl dtc macrocycle (Scheme 6).49 X-ray structure, magnetic susceptibility, ESMS and electrochemical studies all support the tetranuclear catenane dication formulation. The combination of the lability of copper(II) dtc coordinate bonds and favourable copper(II) dtc-copper(III) dtc charge transfer stabilisation effects are responsible for the high yielding formation of the interlocked... 

A chromophore such as the quinone, ruthenium complex, C(,o. or viologen is covalently introduced at the terminal of the heme-propionate side chain(s) (94-97). For example, Hamachi et al. (98) appended Ru2+(bpy)3 (bpy = 2,2 -bipyridine) at one of the terminals of the heme-propionate (Fig. 26) and monitored the photoinduced electron transfer from the photoexcited ruthenium complex to the heme-iron in the protein. The reduction of the heme-iron was monitored by the formation of oxyferrous species under aerobic conditions, while the Ru(III) complex was reductively quenched by EDTA as a sacrificial reagent. In addition, when [Co(NH3)5Cl]2+ was added to the system instead of EDTA, the photoexcited ruthenium complex was oxidatively quenched by the cobalt complex, and then one electron is abstracted from the heme-iron(III) to reduce the ruthenium complex (99). As a result, the oxoferryl species was detected due to the deprotonation of the hydroxyiron(III)-porphyrin cation radical species. An extension of this work was the assembly of the Ru2+(bpy)3 complex with a catenane moiety including the cyclic bis(viologen)(100). In the supramolecular system, vectorial electron transfer was achieved with a long-lived charge separation species (f > 2 ms). 

Keywords Catenane Ir/Ru Light-driven molecular machine Photoinduced Charge Separation Rotaxane Scorpionate... 

In 1989, following extensive preparatory work discussed, the template-directed synthesis of the positively charged [2]-catenane 5 was reported by the Stoddart group (Figure 5.2). Only mild conditions were required, with the crystalline catenane... 

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