Three bilindione isomers: synthesis, characterization and reactivity of biliverdin analogs.
Linear tetrapyrrole is the core structure of light-sensitive native cofactors such as phycocyanobilin, phytochromobilin and bile pigments, which attracts increasing attention in biomimetic chemistry, photochemistry and coordination chemistry. To decipher the relationship between structures and functions, in this work, we firstly reported the synthesis, isolation and characterization of three bilindione isomers (ZZZ, syn, syn, syn 1, EZE, syn, syn, anti 2 and EZE, anti, syn, anti 3) bearing meso-pentafluorophenyl groups. The structures were confirmed by X-ray diffraction and 2-D NMR spectroscopes. More importantly, the interconversion between three isomers under heating and light irradiation was investigated, and isomer 3 was found to be transformed to 1 and 2 more easily, which is in line with the results of DFT calculation. This work provides important insights for understanding the relationship between structures and functions and would be important to further construct metal complexes based on linear tetrapyrrole ligands, which are complementary to well-studied the cyclic analogs such as porphyrin and corroles.
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.|Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, People's Republic of China.
Jun-Fei
JF
Wang
Department of Chemistry, Beijing Key Laboratory of Energy Conversion and Storage Materials, Beijing Normal University, Beijing, 100875, People's Republic of China.
Fang
F
Ma
Department of Chemistry, Beijing Key Laboratory of Energy Conversion and Storage Materials, Beijing Normal University, Beijing, 100875, People's Republic of China.
Hao-Ling
HL
Sun
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China. zhangj271@ucas.ac.cn.
Jing
J
Zhang
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, People's Republic of China. zhangjunlong@pku.edu.cn.
Jun-Long
http://orcid.org/0000-0002-5731-7354
JL
Zhang
D001664:Biliverdine / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism
D008024:Ligands; D001664:Biliverdine
Biliverdin; Linear tetrapyrrole; Reactivity; Structure