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Utilizing suitable precursor molecules, a thermally activated and surface-assisted synthesis results in the formation of defect-free graphene nanoribbons (GNRs), which exhibit electronic properties that are not present in extended graphene. Most importantly, they have a band gap in the order of a few electron volts, depending on the nanoribbon width. In this study, we investigate the electronic structure changes during the formation of GNRs, nitrogen-doped (singly and doubly N-doped) as well as non-N-doped chevron-shaped CGNRs on Au(111). Thus we determine the optical gaps of the precursor molecules, the intermediate nonaromatic polymers, and finally the aromatic GNRs, using high-resolution electron energy loss spectroscopy and density functional theory calculations. As expected, we find no influence of N-doping on the size of the optical gaps. The gap of the precursor molecules is around 4.5 eV. Polymerization leads to a reduction of the gap to a value of 3.2 eV due to elongation and thus enhanced delocalization. The CGNRs exhibit a band gap of 2.8 eV, thus the gap is further reduced in the nanoribbons, since they exhibit an extended delocalized pi-electron system.
A variety of azobenzenes were synthesized to study the behavior of their E and Z isomers upon electrochemical reduction. Our results show that the radical anion of the Z isomer is able to rapidly isomerize to the corresponding E configured counterpart with a dramatically enhanced rate as compared to the neutral species. Due to a subsequent electron transfer from the formed E radical anion to the neutral Z starting material the overall transformation is catalytic in electrons; i.e., a substoichiometric amount of reduced species can isomerize the entire mixture. This pathway greatly increases the efficiency of (photo)switching while also allowing one to reach photostationary state compositions that are not restricted to the spectral separation of the individual azobenzene isomers and their quantum yields. In addition, activating this radical isomerization pathway with photoelectron transfer agents allows us to override the intrinsic properties of an azobenzene species by triggering the reverse isomerization direction (Z -> E) by the same wavelength of light, which normally triggers E -> Z isomerization. The behavior we report appears to be general, implying that the metastable isomer of a photoswitch can be isomerized to the more stable one catalytically upon reduction, permitting the optimization of azobenzene switching in new as well as indirect ways.
Quantum chemical calculations of various azobenzene (AB) derivatives have been carried out with the goal to describe the energetics and kinetics of their thermal cis -> trans isomerization. The effects of substituents, in particular their type, number, and positioning, on activation energies have been systematically studied with the ultimate goal to tailor the switching process. Trends observed for mono- and disubstituted species are discussed. A polarizable continuum model is used to study, in an approximate fashion, the cis -> trans isomerization of azobenzenes in solution. The nature of the transition state(s) and its dependence on substituents and the environment is discussed. In particular for push-pull azobenzenes, the reaction mechanism is found to change from inversion in nonpolar solvents to rotation in polar solvents. Concerning kinetics, calculations based on the Eyring transition state theory give usually reliable activation energies and enthalpies when compared to experimentally determined values. Also, trends in the resulting rate constants are correct. Other computed properties such as activation entropies and thus preexponential rate factors are in only moderate agreement with experiment.
Ingo Schwarz: „etwas hervorzubringen, was meines Königs und meines Vaterlandes werth sein kann“ – Briefe von Alexander von Humboldt an Friedrich Wilhelm III., 1805
Ottmar Ette: Tras la huella de la vida. El proyecto de larga duración „Centro Alejandro de Humboldt. Ciencia en movimiento“ edita los apuntes transdisciplinarios de Humboldt
Horst Bredekamp: Die Amerikanischen Reisetagebücher: ein erster Zugang
Julia Bispinck-Roßbacher: „Zwischen den Zeilen …“ Zur kodikologischen Untersuchung der Amerikanischen Reisetagebücher von Alexander von Humboldt
Tobias Kraft: Humboldts Hefte. Geschichte und Gegenwart von Tagebuch-Forschung und -Rezeption
Dominik Erdmann, Jutta Weber: Nachlassgeschichten – Bemerkungen zu Humboldts nachgelassenen Papieren in der Berliner Staatsbibliothek und der Biblioteka Jagiellońska Krakau
Bewegte Systematik. Alexander von Humboldts „Amerikanische Reisetagebücher“ als Problemfelder der Literaturgeschichte und historischen Epistemologie
Markus Alexander Lenz: Bewegte Systematik. Alexander von Humboldts „Amerikanische Reisetagebücher“ als Problemfelder der Literaturgeschichte und historischen Epistemologie
David Blankenstein, Bénédicte Savoy: Frontale Präsenz - Zu einem unbekannten Porträt Alexander von Humboldts im Besitz des französischen Conseil d’État
Margot Faak: Alexander von Humboldts Amerikareise