期刊
CHEMICAL SCIENCE
卷 12, 期 35, 页码 11864-11872出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1sc02409d
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资金
- Julius-Maximilians-Universitat Wurzburg
- Deutsche Forschungsgemeinschaft (DFG) [MA4471/8-1, GRK 2112]
- Alexander von Humboldt Foundation
- DFG [NI1737/2-1]
- China Scholarship Council
- CoordenacAo de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)
Chemical reduction of the compounds produced monoanions with extensive delocalization and open-shell biradicaloid dianions with temperature-dependent population of triplet states, as confirmed by various experimental techniques.
One-electron chemical reduction of 10-(dimesitylboryl)-N,N-di-p-tolylbenzo[c]phenanthrene-4-amine (3-B(Mes)(2)-[4]helix-9-N(p-Tol)(2)) 1 and 13-(dimesitylboryl)-N,N-di-p-tolyldibenzo[c,g]phenanthrene-8-amine (3-B(Mes)(2)-[5]helix-12-N(p-Tol)(2)) 2 gives rise to monoanions with extensive delocalization over the annulated helicene rings and the boron p(z) orbital. Two-electron chemical reduction of 1 and 2 produces open-shell biradicaloid dianions with temperature-dependent population of the triplet states due to small singlet-triplet gaps. These results have been confirmed by single-crystal X-ray diffraction, EPR and UV/vis-NIR spectroscopy, and DFT calculations.
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