Rotaxane switching

Keywords Electrochemical reactions, Molecular devices, Nanoparticles, Rotaxanes, Switching... 

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. 

Delonno E, Tseng HR, Harvey DD, Stoddard JF, Heat JR (2006) Infrared spectroscopic characterization of [2]rotaxane molecular switch tunnel junction devices. J Phys Chem B 110 7609-7612... 

Keywords Molecular Devices a Molecular Machines a Molecular Wires a Antenna Systems a Molecular Switches a Plug/socket Systems a Pseudorotaxanes a Rotaxanes a Catenanes a Supramolecuiar Chemistry a Photochemistry a Electrochemistry a Luminescence... 

Rotaxanes are made of dumbbell-shaped and ring components which exhibit some kind of interaction originating from complementary chemical properties. In rotaxanes containing two different recognition sites in the dumbbell-shaped component it is possible to switch the position of the ring between the two stations by an external stimu-... 

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. 

Figure 13.8 Schematic operation of a two-station rotaxane as a controllable molecular shuttle, and idealized representation of the potential energy of the system as a function of the position of the ring relative to the axle upon switching off and on station A. The number of dots in each position reflects the relative population of the corresponding coconformation in a statistically significant ensemble. Structures (a) and (c) correspond to equilibrium states, whereas (b) and (d) are metastable states. An alternative approach would be to modify station through an external stimulus in order to make it a stronger recognition site compared to station A.

Figure 13.25 Stmcture formula of rotaxane 284+ and its electrochemically controlled switching process.

The redox-controlled mechanical switching in SAMs of disulfide-functionalized bistable TTF-DMN rotaxanes consisting of cyclophane 124+ and a dumbbell-shaped component containing TTF and DMN stations was also extensively investigated.49... 

Assembling [2] rotaxanes (wheel and axle) can involve three basic processes (Scheme 13). One of these (93CC1269) involves slippage, in which the axle (115) is linked by a 4,4 -bipyridine, and the wheel (116) is a bisparaphenylene-34-crown-10 ether. Heating the two components in acetonitrile at 60°C yields the rotaxane, which can be characterized by FABMS and H and l3C NMR, but extrusion of the wheel occurs at 100°C. In other developments (94NAT(369)133), the pyridine component may be incorporated in the wheel, as in structure (117), where two bipyridinium units are connected by p-xylyl groups, and here the rotaxane acts as molecular switch. At room temperature in acetonitrile the wheel... 

The great variety of incorporable building blocks also offers the synthetic chemist many potential structural and functional design possibilities. The insertion of, e.g., photo-responsive elements, groups with further supramolecular derivatization potential, or sulfonamide units which enable subsequent inter- and intramolecular linkage of catenanes and rotaxanes might render good service in the development of molecular switches [64] and devices [65]. 

This remarkable molecular memory was preceded by two other related examples of addressable molecular electronics from the Stoddart and Heath groups in collaboration with Hewlett-Packard scientists. First in 1999 a [2] rotaxane based system was configured into molecular AND and OR logic gates,63 then in 2000 a [2] catenane based molecular switch was reported.64 The molecular basis for the operation of this switch is the same as in 11.67, namely reorientation in response to reduction of... 

Balzani, V., Venturi, M., Credi, A. Molecular Devices and Machines. A Jorney into the Nanoworld, Wiley-VCH, Weinheim, 2003 b) Feringa, B.L. (ed.), Molecular Switches, Wiley-VCH, Weinheim, 2001 c) Raehm, L., Sauvage, J.-P. Molecular machines and motors based on transition metal-containing catenanes and rotaxanes, Struct. Bond. 99 (2001), 55-78. 

Besides self-assembly on the surface of metals, another example of self-assembly is the formation of Langmuir-Blodgett monolayers on the surface or at the interface of liquids.47,48 One approach to molecular-based electronic devices that has made use of self-assembled Langmuir-Blodgett films is the crossbar-based defect-tolerant approach to molecular computing 49 Rotaxane molecules that depend on physical dislocations within the molecule to produce switching functionality have been designed such that they will... 

One rotaxane molecule is shown in Figure 5.9. This molecule is not expected to demonstrate bistable switching, but is a candidate for a molecular switch that can be configured one time. Note that both ends of the molecule are non-polar hydrocarbon moieties while the center of the molecule is polar. Molecules that have both a non-polar and a polar end, for easier formation of Langmuir-Blodgett films, have been synthesized and tested in devices.51... 

The relative movements of the interlocked components of a [2]catenane and of a [2]rotaxane can be exploited111 121 to perform switching operations at the molecular level. Indeed, there are two states associated with a [2]catenane (Figure 2a) incorporating two different units (0 and 1) in one of its two macrocyclic components. In State 0, the unit 0 is located inside the cavity of the other macrocyclic component and the unit 1 is positioned alongside. In State 1, the unit 1 is located inside and... 

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