Three-dimensional conjugated macrocycle with large polyaromatic blocks constructed by post-π-extension  

作　　者：Shun-He Liu Hao Hou Ze-Ying Deng Xin-Rong Wang Chun Tang Yang-Yang Ju Liu-Bin Feng Yuan-Zhi Tan 

机构地区：[1]State Key Laboratory for Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials,Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China

出　　处：《Science China Chemistry》2020年第11期1626-1631,共6页中国科学（化学英文版）

基　　金：This work was supported by the Ministry of Science and Technology of China(2017YFA0204902,2018YFA0209500);the National Natural Science Foundation of China(21771155,21721001);the Fundamental Research Funds for the Central Universities(20720180035).

摘　　要：Generally,the conjugated homo-macrocycles(CHMs)are synthesized by covalently linking the repeating subunits.However,large subunits are often difficult to conjugate together due to severe stereo-hindrance.Meanwhile,large polyaromatic blocks can not only incorporate its appealing electronic and optical properties into CHMs but also distort the CHMs from planar to three-dimensional(3D)molecular structure.Here we synthesized the 3D CHM composed of large polyaromatic units by post-π-extension.Specifically,cyclo-m-phenylenes,as the cyclic precursor,wereπ-extended by C-C coupling and then subjected to dehydrocyclization,affording cyclo-1,3-dibenzo[e,l]pyrenylenes(CMDP).The structures of CMDPs were unambiguously characterized by single crystal X-ray diffraction,showing a congested and strained 3D conformation,which was also confirmed by theoretical calculations.Compared with the monomer,CMDPs showed redshifted absorption and emission,as well as a ten-fold enhancement in photoluminescence quantum yield,which could be attributed to their 3D conformation.

关 键 词：MACROCYCLE 7r-extension polyaromatic PHOTOLUMINESCENCE 

分 类 号：O641.1[理学—物理化学]