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,lar...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.展开更多
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).
文摘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.
