RESUMEN
Hole-collecting monolayers have drawn attention in perovskite solar cell research due to their ease of processing, high performance, and good durability. Since molecules in the hole-collecting monolayer are typically composed of functionalized π-conjugated structures, hole extraction is expected to be more efficient when the π-cores are oriented face-on with respect to the adjacent surfaces. However, strategies for reliably controlling the molecular orientation in monolayers remain elusive. In this work, multiple phosphonic acid anchoring groups were used to control the molecular orientation of a series of triazatruxene derivatives chemisorbed on a transparent conducting oxide electrode surface. Using infrared reflection absorption spectroscopy and metastable atom electron spectroscopy, we found that multipodal derivatives align face-on to the electrode surface, while the monopodal counterpart adopts a more tilted configuration. The face-on orientation was found to facilitate hole extraction, leading to inverted perovskite solar cells with enhanced stability and high-power conversion efficiencies up to 23.0%.
RESUMEN
Essential components of the human circadian clock, BMAL1 and CLOCK, which are intrinsically disordered transcription factors, were expressed and subjected to a fluorescent in vitro binding assay using an E-box DNA fragment. Screening of a chemical library identified 5,8-quinoxalinedione (1), which was found to inhibit binding of the heterodimer BMAL1/CLOCK to E-box at low micromolar concentrations.
Asunto(s)
Factores de Transcripción ARNTL/antagonistas & inhibidores , Proteínas CLOCK/antagonistas & inhibidores , Relojes Circadianos , ADN/metabolismo , Proteínas Intrínsecamente Desordenadas/antagonistas & inhibidores , Quinoxalinas/farmacología , Factores de Transcripción ARNTL/química , Factores de Transcripción ARNTL/metabolismo , Proteínas CLOCK/química , Proteínas CLOCK/metabolismo , ADN/química , Relación Dosis-Respuesta a Droga , Humanos , Proteínas Intrínsecamente Desordenadas/química , Proteínas Intrínsecamente Desordenadas/metabolismo , Estructura Molecular , Unión Proteica/efectos de los fármacosRESUMEN
A method to obtain an organic mixed-valence state with long-range delocalization is proposed, which enables the selective generation of half-filled (n/2-charged) polycations from linearly bridged oligomers with n electron-donating units. When π-extended phenylenediamine units are connected by meta-xylylene-type spacers, the resulting oligomers adopt non-folded structures in the neutral state owing to the non-conjugating and flexible nature of the spacer, whereas the structure shows a drastic change into a one-dimensional columnar stack upon oxidation to the corresponding half-filled polycations. Although they are nano-sized discrete molecules, they can mimic the electronic structure of crystalline organic conductors in a mixed-valence state. The key for the oligomer design is adoption of the best-matched spacer that facilitates formation of the singly charged pimer in the dichromophoric system whereas the corresponding doubly charged π-dimer is disfavored.
RESUMEN
A perfluorobiphenyl-2,2'-diyl dication and its corresponding dihydrophenanthrene-type electron donor are interconvertible upon two-electron transfer. Redox-triggered C-C bond-formation/cleavage caused a drastic change in the torsion angle of the biphenyl unit. Thus, π-delocalization ON/OFF switching was observed as a change in the UV absorption upon electrolysis of the linearly extended analogue with two phenylethynyl groups. A further extended π-system with a molecular length of ca. 3.5â nm, which has two switching units, was synthesized. Spectroelectrograms as well as voltammetric analyses showed that the two units act nearly simultaneously because of the very small inter-unit electrostatic repulsion in the tetracationic state. Thus, the present pair is a promising candidate as a switching unit for "molecular wires" with controllable π-delocalization, in which a higher ON/OFF ratio of delocalization could be realized by incorporating multiple switching units.
RESUMEN
We have prepared nine structural isomers of a tetrakis(arylethynyl)benzene chromophore functionalized with 4-butoxyphenyl and pyridyl units as the respective donor and acceptor units and examined their steady-state spectroscopic parameters to study how small structural variations effect the electronic absorption and emission spectra. Unlike their 4-dibutylaminophenyl congeners that exhibited dynamic hypsochromic or bathochromic shifts in response to Lewis and Brønsted acids, the current class of compounds simply showed quenched fluorescence upon protonation; only AlCl3 elicited a red-shifted fluorescence response. Computational studies of each system were also performed to provide additional insight into the energy levels and electronic transitions present.
RESUMEN
The gold-catalysed annulation of conjugated alkynes bearing an azido group with arenes gave annulated [c]carbazoles. Using benzene, pyrrole, and indole derivatives as the nucleophiles, benzo[c]-, pyrrolo[2,3-c]-, and indolo[2,3-c]carbazoles were produced, respectively. The reaction proceeded through pyrrole and benzene ring construction accompanied by the formation of two carbon-carbon and one carbon-nitrogen bond and the cleavage of two aromatic C-H bonds. The mechanism of the reaction with pyrrole was investigated by density functional theory calculations. N,N'-dimethylated indolo[2,3-c]carbazole showed dual ultraviolet-visible-near-infrared and fluorescence spectral changes upon electrolysis.
RESUMEN
The title dispiro hydrocarbon 1 was designed as a new electrochromic material. This multiply clamped hexaphenylethane-type electron donor was prepared from 2,2'-diiodobiphenyl via biphenyl-2,2'-diylbis(dibenzotropylium) 22+ salt. X-ray analysis of 1 revealed a highly strained structure as reflected by an elongated "ethane" bond [bond length: 1.6665(17) Å] and nearly eclipsed conformation. The weakened bond was cleaved upon two-electron oxidation to regenerate the deeply colored dication 22+. The reversible interconversion between 1 and 22+ is accompanied not only by a drastic color change but also by C-C bond formation/cleavage. Thus, the voltammogram showed a pair of well-separated redox waves, which is characteristic of "dynamic redox (dyrex)" behavior. The tetrahydro derivative of 1 with two units of spiro(dibenzocycloheptadiene), which suffers from more severe steric congestion, was also prepared. The crystallographically determined bond length for the central C-C bond [1.705(4) Å] is greatest among the values reported for 9,9,10,10-tetraaryl-9,10-dihydrophenanthrene derivatives.