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A key challenge in the field of organic electronics is predicting how chemical structure at the molecular scale determines nature and dynamics of excited states, as well as the macroscopic optoelectronic properties in thin film. Here, the donor–acceptor dyes 4,7‐bis[5‐[4‐(3‐ethylheptyl)‐2,3‐difluorophenyl]‐2‐thienyl]‐2,1,3‐benzothiadiazole (2,3‐FFPTB) and 4,7‐bis[5‐[4‐(3‐ethylheptyl)‐2,6‐difluorophenyl]‐2‐thienyl]‐2,1,3‐benzothiadiazole (2,6‐FFPTB) are synthesized, which only differ in the position of one fluorine substitution. It is observed that this variation in chemical structure does not influence the energetic position of the molecular frontier orbitals or the ultrafast dynamics on the FFPTB backbone. However, it does result in differences at the macroscale, specifically regarding structural and electrical properties of the FFPTB films. Both FFPTB molecules form crystalline films at room temperature, whereas 2,3‐FFPTB has two ordered smectic phases at elevated temperatures, and 2,6‐FFPTB does not display any liquid crystalline phases. It is demonstrated that the altered location of the fluorine substitution allows to control the electrostatic potential along the molecular backbone without impacting molecular energetics or ultrafast dynamics. Such a design strategy succeeds in controlling molecular interactions in liquid crystalline phase, and it is shown that the associated molecular order, or rather disorder, can be exploited to achieve ambipolar transport in FFPTB films. [ABSTRACT FROM AUTHOR]

Blue light receptors using FAD ( BLUFs) facilitate blue light-induced signal transduction via light-induced rearrangement of hydrogen bonds between the flavin chromophore and a conserved glutamine side chain. Here, we investigated the photochemistry of the BLUF domain Slr1694 from Synechocystis sp. in which the glutamine side chain was removed. Without the glutamine, no red-shifted signaling state is formed, but light-induced proton-coupled electron transfer between protein and flavin takes place similarly as for the wild-type protein. However, the lifetime of the neutral flavin semiquinone-tyrosyl radical pair is greatly prolonged from < 100 ps to several nanoseconds, which indicates that the formation of radical intermediates drives the hydrogen bond rearrangement in BLUF photoactivation. Moreover, glutamine plays a central role in the molecular organization of the hydrogen bond network in the flavin-binding pocket, as its removal enhances electron transfer from tyrosine to the excited flavin, and enables competing electron transfer from a nearby tryptophan. [ABSTRACT FROM AUTHOR]

In search of supramolecular antenna systems for light-harvesting applications, we report on a short and effective synthesis of a fused NDI-zinc-salphen-based chromophore (salphen = bis-salicylimide phenylene) and its photophysical properties. A supramolecular recognition motif is embedded into the chromophoric π-system of this compound. The fused π-chromophore behaves as one pigment, absorbs light between 600 and 750 nm and displays a modest Stokes shift. Upon binding pyridines, the compound ( DATZnS) does not change its redox potentials, does not undergo any internal excited state quenching and does not appreciably alter its excited state lifetime. These notable properties define DATZnS as an alternative to porphyrin-based components used in supramolecular light-harvesting architectures. [ABSTRACT FROM AUTHOR]

The phototropins are blue-light receptors that base their light-dependent action on the reversible formation of a covalent bond between a flavin mononucleotide (FMN) cofactor and a conserved cysteine in light, oxygen or voltage (LOV) domains. The primary reactions of the Avena sativa phototropin 1 LOV2 domain were investigated by means of time-resolved and low-temperature fluorescence spectroscopy. Synchroscan streak camera experiments revealed a fluorescence lifetime of 2.2 ns in LOV2. A weak long-lived component with emission intensity from 600 to 650 nm was assigned to phosphorescence from the reactive FMN triplet state. This observation allowed determination of the LOV2 triplet state energy level at physiological temperature at 16600 cm. FMN dissolved in aqueous solution showed pH-dependent fluorescence lifetimes of 2.7 ns at pH 2 and 3.9−4.1 ns at pH 3-8. Here, too, a weak phosphorescence band was observed. The fluorescence quantum yield of LOV2 increased from 0.13 to 0.41 upon cooling the sample from 293 to 77 K. A pronounced phosphorescence emission around 600 nm was observed in the LOV2 domain between 77 and 120 K in the steady-state emission. [ABSTRACT FROM AUTHOR]

The fusion of a naphthalene diimide dye to a zinc–bis‐salicylimide phenylene (salphen) moiety creates an expanded red‐light absorbing chromophore with an embedded metal atom for supramolecular interaction with substituted pyridines. A column‐chromatography‐free preparation of this novel scaffold is described and its photophysical properties are analyzed. For more details, see the Full Paper by K. Lammertsma, R. V. A. Orru et al. on page 10285 ff. [ABSTRACT FROM AUTHOR]