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A novel series of ZnII-trans-A2B2 porphyrins and benzoporphyrins bearing phenyl and thiophene-based meso-substituents was successfully synthesized and characterized by spectroscopic and electrochemical techniques. Systematic comparison among the compounds in this series, together with the corresponding A4 analogs previously studied by our group, led to the understanding of the effects of π-conjugated system extension of a porphyrin core through ß-fused rings, replacement of the phenyl with the thiophene-based meso-groups, and introduction of additional thiophene rings on thienyl substituents on photophysical and electrochemical properties. Oxidative electropolymerization through bithiophenyl units of both A4 and trans-A2B2 analogs was achieved, resulting in porphyrin- and benzoporphyrin-oligothiophene conjugated polymers, which were characterized by cyclic voltammetry and absorption spectrophotometry. Preliminary studies on catalytic performance toward electrochemical reduction of carbon dioxide (CO2) was described herein to demonstrate the potential of the selected compounds for serving as homogeneous and heterogeneous electrocatalysts for the conversion of CO2 to carbon monoxide (CO).

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Modified electrodes using immobilized alcohol dehydrogenase enzymes for the efficient electroreduction of butyraldehyde to butanol are presented as an important step for the utilization of CO2-reduction products. Alcohol dehydrogenase was immobilized, embedded in an alginate-silicate hybrid gel, on a carbon felt (CF) electrode. The application of this enzyme to the reduction of an aldehyde to an alcohol with the aid of the coenzyme nicotinamide adenine dinucleotide (NADH), in analogy to the final step in the natural reduction cascade of CO2 to alcohol, has been already reported. However, the use of such enzymatic reductions is limited because of the necessity of providing expensive NADH as a sacrificial electron and proton donor. Immobilization of such dehydrogenase enzymes on electrodes and direct pumping of electrons into the biocatalysts offers an easy and efficient way for the biochemical recycling of CO2 to valuable chemicals or alternative synthetic fuels. We report the direct electrochemical addressing of immobilized alcohol dehydrogenase for the reduction of butyraldehyde to butanol without consumption of NADH. The selective reduction of butyraldehyde to butanol occurs at room temperature, ambient pressure and neutral pH. Production of butanol was detected by using liquid-injection gas chromatography and was estimated to occur with Faradaic efficiencies of around 40 %.

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During the last years the performance of bulk heterojunction solar cells has been improved significantly. For a large-scale application of this technology further improvements are required. This article reviews the basic working principles and the state of the art device design of bulk heterojunction solar cells. The importance of high power conversion efficiencies for the commercial exploitation is outlined and different efficiency models for bulk heterojunction solar cells are discussed. Assuming state of the art materials and device architectures several models predict power conversion efficiencies in the range of 10-15%. A more general approach assuming device operation close to the Shockley-Queisser-limit leads to even higher efficiencies. Bulk heterojunction devices exhibiting only radiative recombination of charge carriers could be as efficient as ideal inorganic photovoltaic devices.

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We report on C(60) based organic field effect transistors (OFETs) that are well optimized for low voltage operation. By replacing commonly used dielectric layers by thin parylene films or by utilizing different organic materials like divinyltetramethyldisiloxane-bis(benzocyclo-butene) (BCB), low density polyethylene (PE) or adenine in combination with aluminum oxide (AlOx) to form a bilayer gate dielectric, it was possible to significantly increase the capacitance per unit area (up to two orders of magnitude). The assembly of metal-oxide and organic passivation layer combines the properties of the high dielectric constant of the metal oxide and the good organic-organic interface between semiconductor and insulator provided by a thin capping layer on top of the AlOx film. This results in OFETs that operate with voltages lower than 500 mV, while exhibiting field effect mobilities exceeding 3 cm(2) V(-1) s(-1).

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Meyer-Neldel rule for charge carrier mobility measured in C(60)-based organic field-effect transistors (OFETs) at different applied source drain voltages and at different morphologies of semiconducting fullerene films was systematically studied. A decrease in the Meyer-Neldel energy E(MN) from 36 meV to 32 meV was observed with changing electric field in the channel. Concomitantly a decrease from 34 meV to 21 meV was observed too by increasing the grain size and the crystallinity of the active C(60) layer in the device. These empiric findings are in agreement with the hopping-transport model for the temperature dependent charge carrier mobility in organic semiconductors with a Gaussian density of states (DOS). Experimental results along with theoretical descriptions are presented.

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In this feature article, a brief overview over the photoinduced energy and charge transfer mechanisms involving fullerenes will be presented. The photoinduced charge separation between organic donor and acceptor molecules is the basic photophysical mechanism for natural photosynthesis and nearly all organic solar cell concepts. We will give a short introduction to the mechanisms of excited state charge transfer and resonant energy transfer and present examples of relevant applications in organic optoelectronics and photodynamic tumor therapy.

RESUMEN

Bimolecular charge carrier recombination has been clarified in bulk-heterojunction solar cells based on a blend of regioregular poly(3-hexylthiophene) and 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]-methanofullerene using the time-of-flight method. We show how bimolecular recombination influences the charge carrier transport, how it limits the efficiency of low-mobility solar cells, and how to estimate the bimolecular recombination coefficient. We found that bimolecular recombination in these efficient photovoltaic materials is orders of magnitude slower as compared to Langevin recombination expected for low-mobility materials. This effect is inherent to the nanomorphology of the bicontinuous interpenetrating network creating separate pathways for electrons and holes, and paves the way for the fabrication of bulk-heterojunction solar cells where bimolecular recombination is not the limiting factor.

RESUMEN

We conducted a comprehensive Kelvin probe force microscopy (KPFM) study on a classical organic solar cell system consisting of MDMO-PPV/PCBM blends. The KPFM method yields the information of topography and local work function at the nanometer scale. Experiments were performed either in the dark or under cw laser illumination at 442 nm. We identified distinct differences in the energetics on the surface of chlorobenzene and toluene cast blend films. Together with high-resolution scanning electron microscopy (SEM) experiments we were able to interpret the KPFM results and to draw some conclusions for the electron transport toward the cathode in the solar cell configuration. The results suggest that surfaces of toluene cast films exhibit a morphologically controlled hindrance for electron propagation toward the cathode, which is usually evaporated on top of the films in the solar cell device configuration.

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Coherent nuclear motion of the carbon backbone is monitored in real time in substituted poly(phenylene)-vinylene in both excited and ground electronic state using sub-10-fs light pulses. Characteristic features of the intrachain vibrational dynamics are obtained. We observe vibrational dephasing in the excited state within 1 ps (time constant T(2e) approximately 300 fs). These findings are in agreement with the molecular picture for photoexcitation in conjugated polymers.

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Evidence for photoinduced electron transfer from the excited state of a conducting polymer onto buckminsterfullerene, C(60), is reported. After photo-excitation of the conjugated polymer with light of energy greater than the pi-pi* gap, an electron transfer to the C(60) molecule is initiated. Photoinduced optical absorption studies demonstrate a different excitation spectrum for the composite as compared to the separate components, consistent with photo-excited charge transfer. A photoinduced electron spin resonance signal exhibits signatures of both the conducting polymer cation and the C(60) anion. Because the photoluminescence in the conducting polymer is quenched by interaction with C(60), the data imply that charge transfer from the excited state occurs on a picosecond time scale. The charge-separated state in composite films is metastable at low temperatures.