@article{GerlachMonningerSchleieretal.2021, author = {Gerlach, Marius and Monninger, Sophie and Schleier, Domenik and Hemberger, Patrick and Goettel, James T. and Braunschweig, Holger and Fischer, Ingo}, title = {Photoelectron Photoion Coincidence Spectroscopy of NCl\(_{3}\) and NCl\(_{2}\)}, series = {ChemPhysChem}, volume = {22}, journal = {ChemPhysChem}, number = {21}, doi = {10.1002/cphc.202100537}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257322}, pages = {2164-2167}, year = {2021}, abstract = {We investigate NCl\(_{3}\) and the NCl\(_{2}\) radical by photoelectron-photoion coincidence spectroscopy using synchrotron radiation. The mass selected threshold photoelectron spectrum (ms-TPES) of NCl\(_{3}\) is broad and unstructured due to the large geometry change. An ionization energy of 9.7±0.1 eV is estimated from the spectrum and supported by computations. NCl2 is generated by photolysis at 213 nm from NCl\(_{3}\) and its ms-TPES shows an extended vibrational progression with a 90 meV spacing that is assigned to the symmetric N-Cl stretching mode in the cation. An adiabatic ionization energy of 9.94 ± 0.02 eV is determined.}, language = {en} } @article{BergerRueheSchwarzmannetal.2021, author = {Berger, Sarina M. and R{\"u}he, Jessica and Schwarzmann, Johannes and Phillipps, Alexandra and Richard, Ann-Katrin and Ferger, Matthias and Krummenacher, Ivo and Tumir, Lidija-Marija and Ban, Željka and Crnolatac, Ivo and Majhen, Dragomira and Barišić, Ivan and Piantanida, Ivo and Schleier, Domenik and Griesbeck, Stefanie and Friedrich, Alexandra and Braunschweig, Holger and Marder, Todd B.}, title = {Bithiophene-Cored, mono-, bis-, and tris-(Trimethylammonium)-Substituted, bis-Triarylborane Chromophores: Effect of the Number and Position of Charges on Cell Imaging and DNA/RNA Sensing}, series = {Chemistry—A European Journal}, volume = {27}, journal = {Chemistry—A European Journal}, number = {56}, doi = {10.1002/chem.202102308}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256963}, pages = {14057-14072}, year = {2021}, abstract = {The synthesis, photophysical, and electrochemical properties of selectively mono-, bis- and tris-dimethylamino- and trimethylammonium-substituted bis-triarylborane bithiophene chromophores are presented along with the water solubility and singlet oxygen sensitizing efficiency of the cationic compounds Cat\(^{1+}\), Cat\(^{2+}\), Cat(i)\(^{2+}\), and Cat\(^{3+}\). Comparison with the mono-triarylboranes reveals the large influence of the bridging unit on the properties of the bis-triarylboranes, especially those of the cationic compounds. Based on these preliminary investigations, the interactions of Cat\(^{1+}\), Cat\(^{2+}\), Cat(i)\(^{2+}\), and Cat\(^{3+}\) with DNA, RNA, and DNApore were investigated in buffered solutions. The same compounds were investigated for their ability to enter and localize within organelles of human lung carcinoma (A549) and normal lung (WI38) cells showing that not only the number of charges but also their distribution over the chromophore influences interactions and staining properties.}, language = {en} } @article{MukhopadhyaySchleierWirsingetal.2020, author = {Mukhopadhyay, Deb Pratim and Schleier, Domenik and Wirsing, Sara and Ramler, Jaqueline and Kaiser, Dustin and Reusch, Engelbert and Hemberger, Patrick and Preitschopf, Tobias and Krummenacher, Ivo and Engels, Bernd and Fischer, Ingo and Lichtenberg, Crispin}, title = {Methylbismuth: an organometallic bismuthinidene biradical}, series = {Chemical Science}, volume = {11}, journal = {Chemical Science}, number = {29}, doi = {10.1039/D0SC02410D}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-251657}, pages = {7562-7568}, year = {2020}, abstract = {We report the generation, spectroscopic characterization, and computational analysis of the first free (non-stabilized) organometallic bismuthinidene, BiMe. The title compound was generated in situ from BiMe\(_3\) by controlled homolytic Bi-C bond cleavage in the gas phase. Its electronic structure was characterized by a combination of photoion mass-selected threshold photoelectron spectroscopy and DFT as well as multi-reference computations. A triplet ground state was identified and an ionization energy (IE) of 7.88 eV was experimentally determined. Methyl abstraction from BiMe\(_3\) to give [BiMe(_2\)]• is a key step in the generation of BiMe. We reaveal a bond dissociation energy of 210 ± 7 kJ mol\(^{-1}\), which is substantially higher than the previously accepted value. Nevertheless, the homolytic cleavage of Me-BiMe\(_2\) bonds could be achieved at moderate temperatures (60-120 °C) in the condensed phase, suggesting that [BiMe\(_2\)]• and BiMe are accessible as reactive intermediates under these conditions.}, subject = {Photoelektronenspektroskopie}, language = {en} }