@article{HattoriMichailSchmiedeletal.2019, author = {Hattori, Yohei and Michail, Evripidis and Schmiedel, Alexander and Moos, Michael and Holzapfel, Marco and Krummenacher, Ivo and Braunschweig, Holger and M{\"u}ller, Ulrich and Pflaum, Jens and Lambert, Christoph}, title = {Luminescent Mono-, Di-, and Tri-radicals: Bridging Polychlorinated Triarylmethyl Radicals by Triarylamines and Triarylboranes}, series = {Chemistry - A European Journal}, volume = {25}, journal = {Chemistry - A European Journal}, number = {68}, doi = {10.1002/chem.201903007}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-208162}, pages = {15463-15471}, year = {2019}, abstract = {Up to three polychlorinated pyridyldiphenylmethyl radicals bridged by a triphenylamine carrying electron withdrawing (CN), neutral (Me), or donating (OMe) groups were synthesized and analogous radicals bridged by tris(2,6-dimethylphenyl)borane were prepared for comparison. All compounds were as stable as common closed-shell organic compounds and showed significant fluorescence upon excitation. Electronic, magnetic, absorption, and emission properties were examined in detail, and experimental results were interpreted using DFT calculations. Oxidation potentials, absorption and emission energies could be tuned depending on the electron density of the bridges. The triphenylamine bridges mediated intramolecular weak antiferromagnetic interactions between the radical spins, and the energy difference between the high spin and low spin states was determined by temperature dependent ESR spectroscopy and DFT calculations. The fluorescent properties of all radicals were examined in detail and revealed no difference for high and low spin states which facilitates application of these dyes in two-photon absorption spectroscopy and OLED devices.}, language = {en} } @article{ZhangRadackiBraunschweigetal.2021, author = {Zhang, Fangyuan and Radacki, Krzysztof and Braunschweig, Holger and Lambert, Christoph and Ravat, Prince}, title = {Zinc-[7]helicenocyanine and its discrete π-stacked homochiral Dimer}, series = {Angewandte Chemie International Edition}, volume = {60}, journal = {Angewandte Chemie International Edition}, doi = {10.1002/anie.202109380}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256534}, pages = {23656-23660}, year = {2021}, abstract = {In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×10\(^6\) M\(^{-1}\) and 3.42×107 M\(^{-1}\) in THF and DMSO, respectively, indicating remarkable stability of dimer. In addition, Zn\(^{-7}\)HPc exhibited chiral self-sorting behavior, which resulted in preferential formation of a homochiral dimer also in the racemic sample. Two phthalocyanine subunits in the dimeric form strongly communicate with each other as revealed by a large comproportionation constant and observation of an IV-CT band for the thermodynamically stable mixed-valence state.}, language = {en} }