Charge carrier formation in polythiophene/fullerene blend films studied by transient absorption spectroscopy

We report herein a comparison of the photophysics of a series of polythiophenes with ionization potentials ranging from 4.8 to 5.6 eV as pristine films and when blended with 5 wt % 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]C61 (PCBM). Three polymers are observed to give amorphous films, attributed to a nonplanar geometry of their backbone while the other five polymers, including poly(3-hexylthiophene), give more crystalline films. Optical excitation of the pristine films of the amorphous polymers is observed by transient absorption spectroscopy to give rise to polymer triplet formation. For the more crystalline pristine polymers, no triplet formation is observed, but rather a short-lived (approximately 100 ns), broad photoinduced absorption feature assigned to polymer polarons. For all polymers, the addition of 5 wt % PCBM resulted in 70-90% quenching of polymer photoluminescence (PL), indicative of efficient quenching of polythiophene excitons. Remarkably, despite this efficient exciton quenching, the yield of dissociated polymer+ and PCBM- polarons, assayed by the appearance of a long-lived, power-law decay phase assigned to bimolecular recombination of these polarons, was observed to vary by over 2 orders of magnitude depending upon the polymer employed. In addition to this power-law decay phase, the blend films exhibited short-lived decays assigned, for the amorphous polymers, to neutral triplet states generated by geminate recombination of bound radical pairs and, for the more crystalline polymers, to the direct observation of the geminate recombination of these bound radical pairs to ground. These observations are discussed in terms of a two-step kinetic model for charge generation in polythiophene/PCBM blend films analogous to that reported to explain the observation of exciplex-like emission in poly(p-phenylenevinylene)-based blend films. Remarkably, we find an excellent correlation between the free energy difference for charge separation (deltaG(CS)rel) and yield of the long-lived charge generation, with efficient charge generation requiring a much larger deltaG(CS)rel than that required to achieve efficient PL quenching. We suggest that this observation is consistent with a model where the excess thermal energy of the initially formed polaron pairs is necessary to overcome their Coulombic binding energy. This observation has important implications for synthetic strategies to optimize organic solar cell performance, as it implies that, at least devices based on polythiophene/PCBM blend films, a large deltaG(CS)rel (or LUMO level offset) is required to achieve efficient charge dissociation.     

Theoretical investigation of the role of strongly coupled chlorophyll dimers in photoprotection of LHCII

Nonphotochemical quenching is the photoprotection mechanism by which the excess excitation energy absorbed by the light harvesting complex LHCII is dissipated through the protein scaffold as heat. Using the quenched structure of LHCII obtained from crystallographic experiments, the potential quenching of photoexcited excitons by aggregates of chlorophylls is theoretically investigated. In monomeric LHCII there is a hierarchy of length scales resulting in a hierarchy of energy scales that determine the interpigment direct Coulomb coupling. We propose a model whereby eight chlorophylls are coupled quantum mechanically into four dimers, with exciton transfer between these dimers and the remaining six single chlorophylls proceeding incoherently via Forster transfer. The chlorophyll dimer Chl a604-Chl b606 possesses a quasi-parallel geometry, resulting in a weakly dipole-allowed low-lying excited state. This weakly allowed state is accessible via exciton transfer to a higher, strongly allowed state followed by fast vibrational relaxation. This parallel, H-type aggregate can potentially function as an exciton trap. Calculated Forster transfer rates between single chlorophylls and chlorophyll dimers are used in a simulation of exciton transfer in monomeric LHCII to explore this possibility. It is found that Chl a604-Chl b606 has a short-lived enhanced population (on the time scale of approximately picoseconds), but not a long-time resident population. The fluorescence quantum yield of the model was calculated to be phi F = 0.38. Comparison of this result with phi F approximately 0.26 for unquenched LHCII in dilute solution and phi F approximately 0.06 for the highly quenched LHCII crystal reveals that the proposed model does not account for the quenching observed in the LHCII crystal. We therefore conclude that the formation of chlorophyll dimers is not the main cause of excitonic NPQ in LHCII.     

Simulation of organic monolayers as templates for the nucleation of calcite crystals

Living organisms can control the size, shape, and structure of minerals. Attempts to reproduce this biological control in the laboratory often use Langmuir monolayers of long-chain carboxylic acids. We use large-scale molecular dynamics simulations to calculate the interfacial energies of calcite crystals grown on stearic (octadecanoic) acid monolayers. In light of these simulations we discuss the argument that the orientation of the growing mineral is controlled by the organic substrate acting as a template which the mineral must fit in order to grow.     

Total synthesis of (+/-)-cameroonan-7alpha-ol and biomimetic rearrangements to related nopsane sesquiterpenes

A total synthesis of the novel silphinane sesquiterpene alcohol (+/-)-cameroonanol (6-OH) from bicyclic enone 10 was accomplished by conjugate addition of crotylsilane, photochemical hydrobromination, intramolecular alkylation, and hydride reduction. The stereoisomers cameroonan-7beta-ol (18-OH) and 9-epicamerooonanols (19 and 20) were separated from isomer mixtures and the 9-desmethylcameroonanols (21-OH and 22-OH) were obtained by similar means. Solvolysis of 6-OMs and 18-OMs effected skeletal rearrangements to (+/-)-silphiperfol-6-ene (5), (+/-)-prenopsanol (7) and (+/-)-nopsanol (8), and (+/-)-silphiperfolan-7beta-ol (9) in parallel with biogenetic schemes proposed for these naturally occurring sesquiterpenes. The nor analogues 21-OMs and 22-OMs underwent solvolytic rearrangments to a similar set of nor products. The increase in solvolytic rates for the 7beta-mesylates 18-OMs and 22-OMs in comparison to the 7alpha epimers is attributed to concerted antiperiplanar Wagner-Meerwein rearrangements to the prenopsyl and norprenopsyl carbocations. Further analysis of the kinetic data and comparisons with solvolysis rates for the structurally related silphin-1beta-yl and silphin-1alpha-yl mesylates (28 and 29) are presented. The rearrangements observed afford chemical precedent for the biogenetic pathways in the literature for these silphinane sesquiterpenes.     

Synthesis and metal-binding properties of chelating fluorescein derivatives

[reaction: see text] Two routes to highly functionalized metal-chelating fluorescein derivatives have been pursued. Compound 3 is partially quenched by a variety of first-row transition metal ions in aqueous solution, with EC(50) values ranging from 0.4 to 60 microM. Compounds of this type may find application in biological sensing.     

Polarized-neutron scattering study of the cooper-pair moment in Sr2RuO4

We report a study of the magnetization density in the mixed state of the unconventional superconductor Sr2RuO4. On entering the superconducting state we find no change in the magnitude or distribution of the induced moment for a magnetic field of 1 T applied within the Ru O2 planes. Our results are consistent with a spin-triplet Cooper pairing with spins lying in the basal plane. This is in contrast with similar experiments performed on conventional and high- T(c) superconductors.     

Luminescence of insulating Be-doped and Li-doped GaN

Insulating GaN is obtained by doping with Be or Li during crystal growth. These impurities form deep acceptors and are responsible for photoluminescence at 2.16 eV for Be, and at 2.23 eV for Li. A 3.15 eV peak is obtained in insulating GaN when Dy-doping is attempted. Weak electroluminescence was obtained in the Be-doped material.     

Effects of the thickness of birefringent coatings

It is known that birefringent coatings are a powerful experimental technique for the determination of surface strains of metals or other opaque bodies. In this paper the complete state of strain in such a coating is determined for an arbitrary one-dimensional variation of the displacement at the metal surface. It is shown that strain gradients or curvature of the surface have a pronounced effect on the observed birefringence, and must be taken into consideration. This can be done by means of two correction factors derived in the paper which take into account the elastic properties of the coating and its thickness. An experimental procedure is outlined for determining an unknown distribution of strain at the metal surface on the basis of the observed photoelastic pattern.     

Fluorogel Elastomers with Tunable Transparency,Elasticity, Shape‐Memory,and Antifouling Properties

Omniphobic fluorogel elastomers were prepared by photocuring perfluorinated acrylates and a perfluoropolyether crosslinker. By tuning either the chemical composition or the temperature that control the crystallinity of the resulting polymer chains, a broad range of optical and mechanical properties of the fluorogel can be achieved. After infusing with fluorinated lubricants, the fluorogels showed excellent resistance to wetting by various liquids and anti‐biofouling behavior, while maintaining cytocompatiblity.