Band 87, Heft 7

A new family of thermally irreversible photochromic molecules, named “diarylethene,” was serendipitously discovered a quarter of a century ago. The diarylethenes undergo thermally irreversible, fatigue resistant, ultrafast and highly sensitive photochromic reactions. Many of diarylethenes can undergo photochromic reactions even in the single-crystalline phase. The outstanding photochromic performance attracts considerable attention from both scientific and technological points of view, and stimulates research from fundamental physico-chemical aspects to various applications. Here, it is reported how such thermally irreversible photochromic diarylethenes were discovered and developed.

Thermally activated delayed fluorescence (TADF) emitters are third-generation electroluminescent materials that realize highly efficient organic light-emitting diodes (OLEDs) without using rare metals. Here, after briefly reviewing the principles of TADF and its use in OLEDs, we report a sky-blue TADF emitter, 9-(4-(benzo[ d ]thiazol-2-yl)phenyl)- N 3 , N 3 , N 6 , N 6 -tetraphenyl-9 H -carbazole-3,6-diamine (DAC-BTZ). DAC-BTZ is a purely organic donor–acceptor-type molecule with a small energy difference between its lowest excited singlet state and lowest triplet state of 0.18–0.22 eV according to fluorescence and phosphorescence spectra of a DAC-BTZ-doped film. In addition, the doped film exhibits a high photoluminescence quantum yield of 0.82. Time-resolved photoluminescence measurements of the doped film confirm that DAC-BTZ emits TADF. An OLED containing DAC-BTZ as an emitter exhibits a maximum external quantum efficiency (EQE) of 10.3%, which exceeds those obtained with conventional fluorescent emitters (5–7.5%). TADF from DAC-BTZ makes a large contribution to the high EQE of its OLED.

The primary chemical reactions of singlet molecular oxygen with polyunsaturated carotenoids are the focus of this research report. Model compounds that exhibit electronic properties and substituent pattern similar to natural carotenes, xanthophylls or apocarotenoids, respectively, were investigated with regard to photooxygenation reactivity. For dienes and trienes as substrates, high tandem reactivity was observed and hydroperoxy-endoperoxides were isolated as the secondary products of singlet oxygen reaction. The electronic gem-effect on the regioselectivity of the ene reaction is conserved also in vinylogous positions and thus appears to originate from a radical-stabilizing effect. In an attempt to combine different peroxide groups derived from natural products as a tool for new pharmaceutically active products, a dyade synthesis of an artemisinine-safranol with subsequent singlet oxygen addition was realized.

Two electronic push–pull fluorophores consisting of a benzothiadiazole core and a terminal N,N -dimethylamino electron donating group were prepared. The effect of the terminal electron withdrawing group (–NO 2 and –CN) on the spectroscopic, electrochemical, and spectroelectrochemical properties were examined. The fluorophores were solvatochromic with Stokes shifts upward of 9000 cm −1 being observed in aprotic solvents of varying polarity. It was found that the fluorophores fluoresced appreciably (86 % > Φ fl > 18 %) in hexane, toluene, diethyl ether, dichloromethane, ethyl acetate, and THF. The fluorescence was quenched in acetonitrile, acetone, and DMSO. The fluorophores also fluoresced appreciably in thin films when embedded in poly(methyl methacrylate) and poly(dimethylsiloxane) matrices. Protonating the terminal amine with trifluoroacetic acid quenched the intramolecular charge transfer band, although the fluorophores remained fluorescent. The fluorophores could also be reversibly oxidized electrochemically. The resulting oxidized state was visually different than the neutral form. Electrochemical oxidation also led to reversible changes in both the fluorescence wavelength and intensity.

The development of highly sensitive and selective DNA sensors has fuelled applications in a wide range of fields including medical diagnostics, forensics, biodefense, food contamination and environment monitoring. We demonstrate a novel superquenching based DNA sensor with “switch-on” readout using poly( p -phenylenevinylene) (PPV) coated magnetic beads (PPV-MagSi) and quencher functionalized tentacle probes (TP). The sensor design utilizes signal amplification properties of PPV and cooperativity of TPs to monitor hybridization of target oligonucleotides (ONs). The switch-on sensor exhibits excellent sensitivity and selectively discriminates mismatches in the target DNA sequence. Two novel anionic PPVs – poly (6,6′-((2-methyl-5-(( E )-4-(( E )-prop-1-en-1-yl)styryl)-1,4-phenylene)-bis(oxy) dihexanoic acid) ( PMDH ) and poly (6,6′-((2-(( E )-2,5-bis(2-methoxyethoxy)-4-(( E )-prop-1-en-1-yl)styryl)-5-methyl-1,4-phenylene)-bis-(oxy)) di-hexanoic acid) ( PDMonoG ) were tested and compared against each other as part of the sensor design. The employed hairpin TPs possess further advantages of avoiding labelling of target ON, increased selectivity and sensitivity; faster assay time, and capability of magnetically controlled deployment and separation of PPV-MagSi beads.