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Tuning the (Chir)Optical Properties and Squeezing out the Inherent Chirality in Polyphenylene-Locked Helical Carbon Nanorings |
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| Authors: | Jinyi Wang Hong Shi Shengda Wang Xinyu Zhang Pengwei Fang Yu Zhou Prof Gui-Lin Zhuang Prof Xiang Shao Prof Pingwu Du |
| Institution: | 1. Hefei National Laboratory of Physical Science at the Microscale, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui Province, 230026 P.R. China
These authors contributed equally to this work.;2. Department of Chemical Physics, CAS Key Laboratory of Urban Pollutant Conversion, Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui Province, 230026 P.R. China These authors contributed equally to this work.;3. Hefei National Laboratory of Physical Science at the Microscale, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui Province, 230026 P.R. China;4. College of Chemical Engineering, Zhejiang University of Technology, 18, Chaowang Road, Hangzhou, Zhejiang Province, 310032 P.R. China;5. Department of Chemical Physics, CAS Key Laboratory of Urban Pollutant Conversion, Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui Province, 230026 P.R. China |
| Abstract: | Distorting linear polyaromatic hydrocarbons (PAHs) out of planarity affects their physical properties and breaks their symmetry to induce inherent chirality. However, the chirality cannot be achieved in large distorted PAHs-based macrocycles due to a low racemization barrier for isomerization. Herein, we report the precise synthesis and tuning size-dependent (chir)optical properties of a new class of chiral PAHs-containing conjugated macrocycles (cyclon]paraphenylene-2,6-anthrylene, n]CPPAn2,6 ; n=6–8). Their inherent chiralities were squeezed out in small anthrylene-based macrocycles. Efficient resolutions for chiral enantiomers with (P)/(M)-helicity of small 6-7]CPPAn s were achieved by HPLC. Interestingly, these macrocycles showed enriched size-dependent physical, chiral, and (chir)optical properties. Theoretical calculations indicate that these macrocycles have high strain energy (Estrain=60.8 to 73.4 kcal/mol) and very small Egap (～3.0 eV). Notably, these enantiomers showed strong chiroptical properties and dissymmetry factors (|gabs| and |glum|～0.01 for an enantiomer of 6]CPPAn2,6 ), which can give them potential applications in optically active materials. |
| Keywords: | circularly polarized luminescence conjugation inherent chirality macrocycles photophysics |