Wires oligomers

Molecular Wires Oligomers and Polymers with the Poly(triacetylene) (PTA) Backbone... 

Davis WB, Svec WA, Ratner MA et al (1998) Molecular-wire behavior in p-phenylenevi-nylene oligomers. Nature 396 60-63... 

The palladium-catalyzed formation of sulfides can generate polyphenylene sulfide from a dithiol and a dibromoarene, or from 4-bromobenzenethiol (Equation (38)).17 In 1984 Asahi Glass obtained patents for the formation of this polymer in the presence of palladium and nickel catalysts.125,126 In addition, Gingras reported palladium-catalyzed couplings of aryl halides and thiols to form discrete phenylene sulfide oligomers.127,128 A number of polyphenylene sulfide wires, ranging from dimeric to pentameric structures, were prepared by the palladium coupling, albeit in modest yields ... 

Weiss EA, Ahrens MJ, Sinks LE, Gusev AV, Ratner MA, Wasielewski MR (2004) Making a molecular wire charge and spin transport through para-phenylene oligomers. J Am Chem Soc 126(17) 5577-5584... 

Bocian, Lindsey and co-workers studied sandwich complex nanocapacitors comprised of porphyrin and phthalocyanine ligands separated by lanthanide metals [133]. A triple-decker sandwich of phthalocyanine-Eu-phthalocyanine-Eu-porphy-rin, with two phenylethynyl linker wires from the porphyrin, potentially has up to nine accessible oxidation states (—4 to +4). SAMs of monomers, dimers, trimers, and oligomers of this sandwich, anchored at one or both ends by thioacetyl groups, gave charge densities up to 10 10 mol cm-2, electron-transfer rates up to 105 electrons s-1, and charge-dissipation half-lives in the 10-50 s range. 

Oligomer and Film Characterization. Brookfield viscosity measurements were taken on a Model RVTD digital readout viscometer. Samples for Instron testing were prepared on glass plates using 25 or 75 pm (1.0 or 3.0 mil) Byrd film applicator. Coatings for cure speed and MEK double rub (MEKDR) studies were prepared on aluminum Q-Panels using a 40 wire wound rod (100 pm or 4.0 mil). 

A rapid and versatile covalent assembly technique starting from DEE oligomers has provided the 11.9 nm long hexadecameric poly(triacetylene) rod 20.1481 With its linearly conjugated 16 double and 32 triple bonds spanning in-between the terminal silicon atoms, compound 20 is currently the longest linear, fully Jt-conjugated molecular wire without aromatic repeat units in the backbone. 

Redox and Photo Functions of Metal Complex Oligomer and Polymer Wires on the Electrode... 

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. 

In this section, we describe the fabrication of metal complex oligomer and polymer wires composed of bis(terpyridine)metal complexes using the bottom-up method.11 13 This method has an advantage in fabricating organized structures of rigid redox polymer wires with the desired numbers of redox metal complexes. We also present a new electron-transport mechanism applicable to the organized redox polymer wires-coated electrode. 

FIGURE 2. Chemical structures of the ligands and stepwise coordination methods to prepare linear and branched oligomer and polymer wires on an Au/mica or Au/ITO plate. (Reprinted with permission from Ref. 13.)... 

We describe here that the redox oligomer wires fabricated with the stepwise coordination method show characteristic electron transport behavior distinct from conventional redox polymers. Redox polymers are representative electron-conducting substances in which redox species are connected to form a polymer wire.21-25 The electron transport was treated according to the concept of redox conduction, based on the dilfusional motion of collective electron transfer pathways, composed of electron hopping terms and/or physical diffusion.17,18,26-30 In the characterization of redox conduction, the Cottrell equation can be applied to the initial current—time curve after the potential step in potential step chronoamperometry (PSCA), which causes the redox reaction of the redox polymer film ... 

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