Twisted Diindeno-Fused Dibenzo[a,h]anthracene Derivatives and their Dianions |
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Authors: | Prof. Dr. Yanwei Gu Herdya S. Torchon Yikun Zhu Dr. Zheng Wei Dr. Dieter Schollmeyer Dr. Manfred Wagner Prof. Dr. Yong Ni Dr. Zehua Wu Dr. Hao Wu Prof. Dr. Yazhou Zhou Prof. Dr. Zijie Qiu Prof. Dr. Marina A. Petrukhina Prof. Dr. Klaus Müllen |
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Affiliation: | 1. Synthetic Chemistry, Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany;2. Department of Chemistry, University at Albany, State University of New York, 1400 Washington Ave, Albany, NY 12222 USA;3. Department of chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10–14, 55128 Mainz, Germany;4. Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055 P. R. China |
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Abstract: | We report a facile synthesis of diindeno-fused dibenzo[a,h]anthracene derivatives ( DIDBA-2Cl , DIDBA-2Ph , and DIDBA-2H) with different degrees of non-planarity using three substituents (chloro, phenyl, and hydrogen) of various sizes. The planarization of their cores, as evidenced by the decreased end-to-end torsional angles, was confirmed by X-ray crystallography. Their enhanced energy gaps with twisting were investigated by a combination of spectroscopic and electrochemical methods with density functional theory, which showed a transition from singlet open-shell to closed-shell configuration. Moreover, their doubly reduced states, DIDBA-2Ph 2− and DIDBA-2H 2−, were achieved by chemical reduction. The structures of dianions were identified by X-ray crystallographic analysis, which elucidated that the electron charging further distorted the backbones. The electronic structure of the dianions was demonstrated by experimental and theoretical approaches, suggesting decreased energy gaps with larger non-planarity, different from the neutral species. |
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Keywords: | Aromaticity Dianions Diradicals Fused-Ring Systems Twisted Structures |
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