Controlling Interchromophore Coupling in Diamantane-Linked Pentacene Dimers To Create a "Binary" Pair.

Two isomeric pentacene dimers, each linked by a diamantane spacer, have been synthesized. These dimers are designed to provide experimental evidence to support quantum mechanical calculations, which predict the substitution pattern on the carbon-rich diethynyldiamantane spacer to be decisive in controlling the interpentacene coupling. Intramolecular singlet fission (-SF) serves as a probe for the existence and strength of the electronic coupling between the two pentacenes, with transient absorption spectroscopy as the method of choice to characterize -SF.

Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer.

Triplet dynamics in singlet fission depend strongly on the strength of the electronic coupling. Covalent systems in solution offer precise control over such couplings. Nonetheless, efficient free triplet generation remains elusive in most systems, as the intermediate triplet pair (T T ) is prone to triplet-triplet annihilation due to its spatial confinement.

Tetracene Dimers: A Platform for Intramolecular Down- and Up-conversion.

Photon energy conversion can be accomplished in many different ways, including the two opposing manners, down-conversion (i.e., singlet fission, SF) and up-conversion (i.

Sensitized Singlet Fission in Rigidly Linked Axial and Peripheral Pentacene-Subphthalocyanine Conjugates.

The goal of harnessing the theoretical potential of singlet fission (SF), a process in which one singlet excited state is split into two triplet excited states, has become a central challenge in solar energy research. Covalently linked dimers provide crucial models for understanding the role of chromophore arrangement and coupling in SF. Sensitizers can be integrated into these systems to expand the absorption bandwidth through which SF can be accessed.

A Geometrically Well-Defined and Systematically Tunable Experimental Model to Transition from Planar to Mesoporous Perovskite Solar Cells.

A series of perovskite solar cells with systematically varying surface area of the interface between n-type electron conducting layer (TiO) and perovskite are prepared by using an ordered array of straight, cylindrical nanopores generated by anodizing an aluminum layer evaporated onto a transparent conducting electrode. A series of samples with pore length varied from 100 to 500 nm are compared to each other and complemented by a classical planar cell and a mesoporous counterpart. All samples are characterized in terms of morphology, chemistry, optical properties, and performance.

Green-up selection by red deer in heterogeneous, human-dominated landscapes of Central Europe.

The forage maturation hypothesis (FMH) assumes that herbivores cope with the trade-off between digestibility and biomass in forage by selecting vegetation at intermediate growth. The green wave hypothesis (GWH) extends the FMH to suggest how spatiotemporal heterogeneity in plant quality shapes migratory movements of herbivores. Growing empirical support for these hypotheses mainly comes from studies in vast landscapes with large-scale habitat heterogeneity.

Parallel versus Twisted Pentacenes: Conformational Impact on Singlet Fission.

We placed two pentacene chromophores at the termini of a diacetylene linker to investigate the impact of excitation wavelength, conformational flexibility, and vibronic coupling on singlet fission. Photoexcitation of the low-energy absorption results in a superposed mixture of states, which transform on an ultrafast time-scale into a spin-correlated and vibronically coupled/hot delocalized triplet pair (TT). Regardless of temperature, the lifetime for (TT) is less than 2 ps.

How To Make Nitroaromatic Compounds Glow: Next-Generation Large X-Shaped, Centrosymmetric Diketopyrrolopyrroles.

Red-emissive π-expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three-step strategy involving the preparation of diketopyrrolopyrrole followed by N-arylation and subsequent intramolecular palladium-catalyzed direct arylation. Comprehensive spectroscopic assays combined with first-principles calculations corroborated that both N-arylated and fused DPPs reach a locally excited (S ) state after excitation, followed by internal conversion to states with solvent and structural relaxation, before eventually undergoing intersystem crossing. Only the structurally relaxed state is fluorescent, with lifetimes in the range of several nanoseconds and tens of picoseconds in nonpolar and polar solvents, respectively.

Singlet Fission in Pyrene-Fused Azaacene Dimers.

Singlet fission has emerged as a promising strategy to avoid the loss of extra energy through thermalization in solar cells. A family of dimers consisting of nitrogen-doped pyrene-fused acenes that undergo singlet fission with triplet quantum yields as high as 125 % are presented. They provide new perspectives for nitrogenated polycyclic aromatic hydrocarbons and for the design of new materials for singlet fission.

Davydov splitting and singlet fission in excitonically coupled pentacene dimers.

Singlet fission (SF) allows two charges to be generated from the absorption of a single photon and is, therefore, potentially transformative toward improving solar energy conversion. Key to the present study of SF is the design of pentacene dimers featuring a xanthene linker that strictly places two pentacene chromophores in a rigid arrangement and, in turn, enforces efficient, intramolecular π-overlap that mimics interactions typically found in condensed state (, solids, films, ). Inter-chromophore communication ensures Davydov splitting, which plays an unprecedented role toward achieving SF in pentacene dimers.

p-Doping of graphene in hybrid materials with 3,10-diazapicenium dications.

,'-Didodecyl-substituted 3,10-diazapicenium salts featuring bromide and hexafluorophosphate counterions have been designed as novel dopants to realize individualized graphene sheets in a series of cutting edge experiments and to intrinsically stabilize them p-doping. Importantly, electrochemical studies revealed two consecutive irreversible one-electron reductions of the ,'-didodecyl-substituted 3,10-diazapicenium salts to yield the corresponding radical cation and neutral quinoidal species. Formation of both species was accompanied by characteristic changes in the absorption spectra.

Measuring corticosterone metabolites in droppings of capercaillies (Tetrao urogallus).

The capercaillie (Tetrao urogallus), the largest grouse species in the world, is decreasing in numbers in major parts of its distribution range. Disturbances by human outdoor activities are discussed as a possible reason for this population decline. An indicator for disturbances is the increase of the glucocorticoid corticosterone, a stress hormone, which helps to cope with life-threatening situations.