The intermolecular arrangement in the solid state and the consequences on the optical and photophysical properties are studied on different derivatives of oligophenylenevinylenes by UV/VIS absorption and angular-resolved polarized fluorescence spectroscopy. Unsubstituted distyrylbenzene (DSB) organizes in a herringbone manner, with the long axes of the molecules oriented in parallel, but the short axes almost perpendicular to each other. Fluorinated distyrylbenzene (F(12)DSB) as well as the DSB:F(12)DSB cocrystals prefer cofacial pi-stacking in the solid state. For all structures, the consequence of the parallel alignment of the transition moments is a strongly blueshifted H-type absorption spectrum and a low radiative rate constant k(F). Significant differences are observed for the emission spectra: the perpendicular arrangement of the short axes in DSB crystals leads to only very weak intermolecular vibronic coupling. Hence the emission spectrum is well structured, very similar to the one in solution. For F(12)DSB and DSB:F(12)DSB, the cofacial arrangement of the adjacent molecules enables strong intermolecular vibronic coupling of adjacent molecules. Thus, an unstructured and strongly redshifted excimerlike emission spectrum is observed. The differences in the electronic nature of the excited states are highlighted by quantum-chemical calculations, revealing the contribution of interchain excitations to the electronic transitions.

No abstract

Significant progress is being made in the photovoltaic energy conversion using organic semiconducting materials. One of the focuses of attention is the morphology of the donor−acceptor heterojunction at the nanometer scale, to ensure efficient charge generation and loss-free charge transport at the same time. Here, we present a method for the controlled, sequential design of a bilayer polymer cell architecture that consists of a large interface area with connecting paths to the respective electrodes for both materials. We used the surface-directed demixing of a donor conjugated/guest polymer blend during spin coating to produce a nanostructured interface, which was, after removal of the guest with a selective solvent, covered with an acceptor layer. With use of a donor poly(p-phenylenevinylene) derivative and the acceptor C60 fullerene, this resulted in much-improved device performance, with external power efficiencies more than 3 times higher than those reported for that particular material combination so far.

Two new, fully conjugated polymeric cyanine dyes based on trimethine and heptamethine moieties have been synthesized. Both polymers were characterized by gel permeation chromatography, UV‐vis and IR spectroscopy, elementary analysis and cyclic voltammetry. The structure of one material could be confirmed with NMR spectroscopy. Upon head‐to‐tail coupling of the dye moieties distinct bathochromic shifts up to 159 nm were observed for the polymers which absorb solely in the near infrared (NIR) region with maxima up to 1 002 nm and very high molar absorption coefficients. This highly efficient absorption in the NIR spectral domain combined with the strong electron accepting properties makes these dyes interesting candidates for many optical applications; investigations on photovoltaic devices based on polymeric cyanine dye/C60 heterojunctions identify one of these possibilities.

Non‐crystalline anthracene‐containing binaphthol chromophores were synthesized, characterized, and used in the fabrication of organic light‐emitting diodes (OLEDs). Specifically, the target molecules were 2,2′‐dihexyloxy‐1,1′‐binaphthol‐6,6′‐bisanthracene (BA1) and 2,2′‐dimethoxyy‐1,1′‐binaphthol‐6,6′‐bisanthracene (BA2). Molecules BA1 and BA2 provide amorphous solids, as determined by their glass‐transition temperature (Tg) measured by differential scanning calorimetry (DSC). Efficient multilayer OLEDs containing BA1 and BA2 were fabricated by evaporation techniques. Differences in the electroluminescence frequencies of these devices suggests that the degree of alkoxide substitution controls the mobility within the binaphthol material, and therefore the recombination region in the device. Compound BA2 can also be used to dope CBP ((4,4′‐bis(carbazol‐9‐yl)biphenyl)) in the fabrication of highly efficient OLEDs.

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of B30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of B1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport. IntroductionThe potential of cheap photovoltaics is fueling the interest in organic semiconductors. [1][2][3][4] State-of-the-art devices are made from a combination of electron-donor and electron-acceptor (D-A) materials, sandwiched between metallic electrodes. 5 Photoexcitation of either of the two components leads to an exciton that can dissociate into free charge carriers at the D-A interface. 6 After charge separation, electrons and holes are transported via drift and diffusion processes to the electrodes, where they are collected, giving rise to an electric current. 2 Device efficiency is determined by the short-circuit current (J sc ), the open-circuit voltage (V oc ), and the fill factor (FF) via Z = (J sc V oc FF)/P, where P is the incident optical power. The FF is a measure of the ability to transport and extract charges when the applied voltage approaches V oc ; J sc is determined by the fraction of absorbed photons from the incident sunlight as well as by the ability to create charges via exciton dissociation at the D-A interface. Consensus has now been reached that V oc correlates with the energy difference (E D ) between the highest occupied molecular orbital (HOMO) of the donor and the lowest unoccupied molecular orbital (LUMO) of the acceptor. [7][8][9] It follows that both J sc and V oc depend on the donor and acceptor energy levels and their offsets at the heterojunction (for illustration, see Fig. 1c). A high V oc requires a high E D . However, this implies that the HOMO-HOMO (E HH ) and LUMO-LUMO (E...

Conjugated polymers and oligomers can serve as highly responsive fluorescent reporters for biosensor applications. However, their optical properties in aqueous media are highly dependent upon environmental conditions. The structure of the paracyclophane framework provides a platform for designing optical reporters that show little sensitivity to surfactants, and thus is well-suited for fluorescent assays. The permanent intramolecular delocalization through the paracyclophane core dominates intermolecular perturbations in spontaneously formed aggregates.

No abstract