Switchable molecular wires

The insertion of a photosensitive group or of a redox active unit into the push-pull system 1 yields switchable molecular wires and push-pull molecules that contain a photo-switch or a redox switch S, as represented in 4. Compounds of such type containing for instance electroactive ferrocene groups and photosensitive metal complexes, have been synthesized. Some of them are shown in series 5 (Marczinke, B. Przibilla, K.J. Lehn, J.-M., unpublished data). 

Like in other chiroptical switches (Section 5.3.1), solvent polarity was found to play an important role. Diastereoselective cyclization was observed in THF and toluene, but not in nonpolar solvents such as n-hexane. Upon photoexcitation, diarylethenes 24 (Scheme 11) can adopt a planar and a twisted conformation, and photocyclization only proceeds through the planar conformation. In the case of chiral diarylethene 27a, there are two diastereomeric planar conformations leading to the diastereomers of the cyclic product 27b. The stereoselectivity in the photocyclization process is enhanced because of a decrease in the excited state energy of the unreactive twisted form, providing a relaxation pathway for the less favorable planar diastereoisomer in more polar solvents. Chiral photochromic diarylethenes are among the most prominent photoswitches known today, featuring nondestructive read-out, excellent reversibility, and the potential for construction of switchable molecular wires and modulation of liquid crystalline phases (see Section 5.5.3).[40,411... 

A three-level switching device has been demonstrated in which photochromic properties are used to control electrical properties, and vice versa. Such a system has been realized in the form of thiophene bisphenol [90, 91]. Conversion of the open (8a) to the closed (8b) form of the thiophene was achieved by absorption of 312 nm light, and revered by absorption of 600 nm light. The bisphenol oxidation occurs at +0.735 V (vs. SCE), forming the closed-ring bisquinone, compound 8c. This species has large absorptions at 400 and 534 nm. The optical properties of the quinone phenol couple have previously been used in a bianthrone-based system [87]. The bisquinone (8c) cannot be converted to the open thiophene, and locks the system in the closed form. The thiophene has also been incorporated as a component in two-level molecular switches [99, 128] and switchable molecular wires [30]. 

These types of switchable electrode surfaces have been used to selectively pattern two different cell populations onto a surface [151] and additionally these surfaces can selectively release different cells at different applied potentials [152]. However, it is important to recognize that electrochemically switching a surface from inactive to conjugation and active to conjugation has been well explored with nitro-terminated aryl diazonium salts. In such studies, the application where very anodic potential resulted in a six-electron reduction to an amine [139], to which proteins could be attached [153-155]. The key difference is that the interaction of the biological medium with the surface is controlled by the presence of the antifouling layer. In many ways these electrode surfaces developed by Mrksich and coworkers [150-152, 156] are very similar to the antifouling surfaces with molecular wires discussed in Section 1.4.2 [131, 132, 138, 142]. In both cases the electrode is... 

Sendt K, Johnston LA, Hough WA, Crossley MJ, Hush NS, Reimers JR (2002) Switchable electronic coupling in model oligopoiphyrin molecular wires examined through the measurement and assignment of electronic absorption spectra. J Am Chem Soc 124(31) 9299-9309. doi 10.1021/ja020081u... 

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