Rectangular Holes in Porphyrin Isomers Act As Mono- and Binucleating Ligands: Stereochemistry of Mono- and Diboron Porphycenes and Their Protonation Behaviors
- Ning XuNing XuDepartment of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanMore by Ning Xu
- ,
- Toshikazu Ono*Toshikazu Ono*E-mail: [email protected]Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanCenter for Molecular Systems (CMS), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanMore by Toshikazu Ono
- ,
- Yoshitsugu MoritaYoshitsugu MoritaDepartment of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, JapanMore by Yoshitsugu Morita
- ,
- Teruyuki KomatsuTeruyuki KomatsuDepartment of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, JapanMore by Teruyuki Komatsu
- , and
- Yoshio Hisaeda*Yoshio Hisaeda*E-mail: [email protected]Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanCenter for Molecular Systems (CMS), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanMore by Yoshio Hisaeda
Abstract
The first boron complexes of porphycenes, structural isomers of porphyrin, are reported. They are synthesized in good yields by reacting the free-base porphycene ligands with BF3·Et2O through a microwave-assisted method. Depending on the substituent group of porphycenes, two different coordination structures, mono- and diboron porphycenes, are obtained simultaneously. The single crystal structures and DFT calculations suggest that the boron atom of the monoboron porphycene is favorably coordinated on the dipyrroethene site, and the regioisomer of diboron porphycene is of cisoid stereochemistry, which is more stable than transoid. We also investigate the protonation behavior of boron porphycene complexes. Diboron porphycene does not undergo protonation, whereas monoboron porphycene undergoes protonation at the nonboron coordinating pyrroline site, resulting in a red shift in both absorption and emission spectra. Protonation and deprotonation of monoboron porphycene can be reversibly triggered using acids and bases.
Cited By
This article is cited by 4 publications.
- Changjiang Yu, Yingzhu Sun, Xingbao Fang, Jiazhu Li, Qinghua Wu, Weibin Bu, Xing Guo, Hua Wang, Lijuan Jiao, Erhong Hao. Aromatic-Ring-Fused BOPPY Fluorophores: Synthesis, Spectral, Redox Properties, and Bioimaging Application. Inorganic Chemistry 2022, 61 (42) , 16718-16729. https://doi.org/10.1021/acs.inorgchem.2c02517
- Avisikta Sinha, Tamal Chatterjee, Mangalampalli Ravikanth. Synthesis and properties of boron porphyrinoids. Coordination Chemistry Reviews 2022, 465 , 214574. https://doi.org/10.1016/j.ccr.2022.214574
- Sameeta Sahoo, Pradeepta K. Panda. β,β′-fusion induced unique out-of-plane platinum(II) complexation in porphycene. Inorganica Chimica Acta 2022, 530 , 120679. https://doi.org/10.1016/j.ica.2021.120679
- Zhi Zhang, Taro Fujioka, Taro Koide, Yoshio Yano, Toshikazu Ono, Yoshio Hisaeda. Synthesis of first antimony porphycene and electrocatalytic hydrogen evolution driven by ligand-centered reduction. Bulletin of the Chemical Society of Japan 2021, https://doi.org/10.1246/bcsj.20210177