Size-Selective Diffusion of Ferrocenes through Molecular Voids Created by Photolysis of Copolymeric Films

Gould, Sharon; Gray, Kimberley H.; Linton, Richard W.; Meyer, Thomas J.

doi:10.1021/j100043a053

Cited by 11 publications

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“…Electropolymerization has been used to create a variety of film structures, some of which could find application in assembling elements for artificial photosynthesis. They include (1) bilayers by sequential polymerization of [Ru(vbpy) 3 ] 2+ , followed by [Os(vbpy) 3 ] 2+ , for example, in which rectification (electron transfer in one direction) has been observed; (2) pH-induced electron transfer from an outer film−solution interface across an inner film layer; (3) photocurrent effects and electroluminescence; (4) electropolymerized overlayer stabilization of an adsorbed chromophore on TiO 2 ; (5) creation of molecular voids for size-selective diffusion and micron-level image formation; ,− (6) formation and reactivity of catalytically active Ru IV O and ORu VI O sites imbedded in film structures with spatial control; and (7) electropolymerization of electro- and photoactive films of PS-derivatized “macromers”, containing multiple linked Ru(vbpy) complexes, and of large, preformed molecular assemblies. , …”

Section: Assembling the Assemblies In Device-like Configurationsmentioning

confidence: 99%

Chemical Approaches to Artificial Photosynthesis. 2

2005

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The goal of artificial photosynthesis is to use the energy of the sun to make high-energy chemicals for energy production. One approach, described here, is to use light absorption and excited-state electron transfer to create oxidative and reductive equivalents for driving relevant fuel-forming half-reactions such as the oxidation of water to O2 and its reduction to H2. In this "integrated modular assembly" approach, separate components for light absorption, energy transfer, and long-range electron transfer by use of free-energy gradients are integrated with oxidative and reductive catalysts into single molecular assemblies or on separate electrodes in photelectrochemical cells. Derivatized porphyrins and metalloporphyrins and metal polypyridyl complexes have been most commonly used in these assemblies, with the latter the focus of the current account. The underlying physical principles--light absorption, energy transfer, radiative and nonradiative excited-state decay, electron transfer, proton-coupled electron transfer, and catalysis--are outlined with an eye toward their roles in molecular assemblies for energy conversion. Synthetic approaches based on sequential covalent bond formation, derivatization of preformed polymers, and stepwise polypeptide synthesis have been used to prepare molecular assemblies. A higher level hierarchial "assembly of assemblies" strategy is required for a working device, and progress has been made for metal polypyridyl complex assemblies based on sol-gels, electropolymerized thin films, and chemical adsorption to thin films of metal oxide nanoparticles.

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Section: Assembling the Assemblies In Device-like Configurationsmentioning

confidence: 99%

Chemical Approaches to Artificial Photosynthesis. 2

2005

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“…This includes heterogeneous, multilayered structures containing spatially discrete, redox-active regions, and molecular composites with different molecules in the same region. Procedures have been described for imaging and the creation of vertical columnar structures and active microstructures for catalysis, electrochromism, and “molecular filtering”. ,− …”

Section: Discussionmentioning

confidence: 99%

Electropolymerized Films of Macromeric Assemblies

et al. 1998

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The polymer poly[4-(2-aminoethyl)styrene], prepared by living anionic polymerization, has been derivatized by amide coupling to [Ru(II)(vbpy)(2)(4-CO(2)H-4'-CH(3)bpy)](2+) (vbpy is 4-vinyl-4'-methyl-2,2'-bipyridine; 4-CO(2)H-4'-CH(3)bpy is 4-methyl-2,2'-bipyridine-4'-carboxylic acid). The resulting "macromer" can be electropolymerized on a variety of electrode materials by reductive electropolymerization. Compared to similar films of poly[Ru(II)(vbpy)(3)](PF(6))(2): (1) the macromeric films are considerably rougher, apparently having open, local microporous structures; (2) they undergo comparable rates of intrafilm charge transfer; and (3) they have shortened metal-to-ligand charge transfer (MLCT) excited state lifetimes, apparently due to quenching by film-based trap sites. Stable films of a mixed polymer have also been prepared by sequential addition of [Ru(II)(bpy)(2)(4-CO(2)H-4'-CH(3)bpy)](2+) and then the vbpy derivative.

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“…One could conjecture that our probes can reach the ITO electrode by diffusing through pinholes or defects . However, the observed selectivity rules out this possibility because mass transport through pinholes or film imperfections is believed to be independent of the dimensions of the diffusing molecules. , …”

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“…The rational design, preparation, and properties of porous materials might lead to new applications in energy storage, separation of gases, heterogeneous catalysis, and sensing. , Size-selective transport of small molecules has been achieved with surface-confined materials having cavities that reflect their molecular dimensions. , However, controlling pore structures and understanding their size-exclusion properties remain a challenge . Equally important are the electron transfer (ET) properties of surface-confined molecular materials.…”

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confidence: 99%