@article{MaassUtechtStremlauetal.2017, author = {Maass, Friedrich and Utecht, Manuel Martin and Stremlau, Stephan and Gille, Marie and Schwarz, Jutta and Hecht, Stefan and Klamroth, Tillmann and Tegeder, Petra}, title = {Electronic structure changes during the on-surface synthesis of nitrogen-doped chevron-shaped graphene nanoribbons}, series = {Physical review : B, Condensed matter and materials physics}, volume = {96}, journal = {Physical review : B, Condensed matter and materials physics}, publisher = {American Physical Society}, address = {College Park}, issn = {2469-9950}, doi = {10.1103/PhysRevB.96.045434}, pages = {7}, year = {2017}, abstract = {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.}, language = {en} } @article{GouletHanssensUtechtMutrucetal.2017, author = {Goulet-Hanssens, Alexis and Utecht, Manuel and Mutruc, Dragos and Titov, Evgenii and Schwarz, Jutta and Grubert, Lutz and Bleger, David and Saalfrank, Peter and Hecht, Stefan}, title = {Electrocatalytic Z -> E Isomerization of Azobenzenes}, series = {Journal of the American Chemical Society}, volume = {139}, journal = {Journal of the American Chemical Society}, number = {1}, publisher = {American Chemical Society}, address = {Washington}, issn = {0002-7863}, doi = {10.1021/jacs.6b10822}, pages = {335 -- 341}, year = {2017}, abstract = {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.}, language = {en} }