Redox metal complex conduction

Keywords n-d interaction, 3d transition metal, Electronic conductivity, Magnetism, Redox-active complexes, TTF... 

There are basically two approaches to the synthesis of enantiomerically pure alcohols (i) kinetic resolution of the racemic alcohol using a hydrolase (lipase, esterase or protease) or (ii) reduction mediated by a ketoreductase (KRED). Both of these processes can be performed as a cascade process. The first approach can be performed as a dynamic kinetic resolution (DKR) by conducting an enzymatic transesterification in the presence of a redox metal [e.g. a Ru(ll) complex] to catalyze in situ racemization of the unreacted alcohol isomer [11] (Scheme 6.1). We shall not discuss this type of process in any detail here since it forms the subject of Chapter 1. 

In the last decade, there has been a large number of reports on synthetic macro-molecule-metal complexes concerning their complexation, catalytic activities, redox reactions, adsorptions of gaseous molecules and metal ions, photochemical behavior, biochemical effects, modified electrodes, semiconductive and conductive materials, and so on. 

II. BOTTOM-UP FABRICATION OF REDOX-CONDUCTING METAL COMPLEX OLIGOMERS ON AN ELECTRODE SURFACE AND THEIR REDOX CONDUCTION BEHAVIOR 389... 

III. PHOTOELECTRIC CONVERSION SYSTEM USING PORPHYRIN AND REDOX-CONDUCTING METAL COMPLEX WIRES 401... 

In this chapter, we describe three different systems with which to construct electro- and photo-functional molecular assemblies on electrode surfaces. The first is the bottom-up fabrication of redox-conducting metal complex oligomers on an electrode surface and their characteristic redox conduction behavior, distinct from conventional redox polymers.11-13 The second is a photoelectric conversion system using a porphyrin and redoxconducting metal complex.14 The third is the use of a cyanobacterial photosystem I with molecular wires for a biophotosensor and photoelectrode.15 16 These systems will be the precursors of new types of molecular devices working in electrolyte solution. 

A. Bottom-Up Fabrication of the Porphyrin-Terminated Redox-Conducting Metal Complex Film on ITO... 

A great amount of research has focused on the electronic structure, spectroscopy, redox properties, and conductivity of homoleptic bis(l,2-dithiolene) complexes of c transition metal ions (51). The compounds are often highly... 

Hybrid materials which combine the electronic conductivity of thiophene-conjugated polymers and the redox and optical properties of metal complexes are being developed to take advantage of synergistic electronic interactions. 

Most studies indicate that the metal has the greatest effect on the properties of the polymer when it is part of the backbone, rather than a sidegroup. The direct coupling of the metal orbitals with the Tr-orbitals of the conjugated polymer may allow redox-matching to enhance the conductivity and perturb the band structure of the polymer. However, it is often synthetically easier to add the metal center as a side chain of a known polymer (e.g., on PPV) than to develop new polymerization procedures for the metal complex. 

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