S-Shaped Helical Singlet Diradicaloid and Its Transformation to Circumchrysene via a Two-Stage Cyclization

Hu, Jinlian1; Xiang, Qin1; Tian, Xiaoqi1; Ye, Lei2; Wang, Yanpei3; Ni, Yong3; Chen, Xing1; Liu, Yuxia4; Chen, Guang4; Sun, Zhe1

2024-04-03

10.1021/jacs.3c11585

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Polycyclic hydrocarbons with diradical and polyradical characters usually display unique reactivities in ring-cyclization reactions. However, such reactions are rarely used to construct pi-extended polycyclic aromatic hydrocarbons. Here, we describe the synthesis of an S-shaped doubly helical singlet diradicaloid compound and its facile transformation into an unprecedented circumchrysene via a two-stage ring cyclization, which includes: (1) an eletrocylization from diradicaloid precursor and (2) a Scholl reaction. The reaction mechanism was investigated through in situ spectroscopic studies, assisted by theoretical calculations. This reaction sequence yields an optically resolved pi-extended [5]helicene derivative with a fluorescence quantum yield up to 85% and a circularly polarized luminescence brightness up to 6.05 M-1 cm(-1) in the far-red to near-infrared regions. This sequence also yielded a highly delocalized circumchrysene molecule, exhibiting large electron delocalization, moderate fluorescence quantum yield, and multistage redox properties.

SCI ; IC ; EI

英语

其他

National Natural Science Foundation of China["21971187","22222110","22371206"] ; National Natural Science Foundation of China[19JCJQJC62700]

Chemistry

Chemistry, Multidisciplinary

WOS:001196479800001

AMER CHEMICAL SOC

Web of Science

1.Tianjin Univ, Haihe Lab Sustainable Chem Transformat, Dept Chem, Inst Mol Plus, Tianjin 300072, Peoples R China
2.Tsinghua Univ, Inst Biopharmaceut & Hlth Engn, Tsinghua Shenzhen Int Grad Sch, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
4.Shaanxi Univ Sci & Technol, Coll Chem & Chem Engn, Shaanxi Key Lab Chem Addit Ind, Key Lab Chem Addit China Natl Light Ind, Xian 710021, Peoples R China

Hu, Jinlian,Xiang, Qin,Tian, Xiaoqi,et al. S-Shaped Helical Singlet Diradicaloid and Its Transformation to Circumchrysene via a Two-Stage Cyclization[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(15).

Hu, Jinlian.,Xiang, Qin.,Tian, Xiaoqi.,Ye, Lei.,Wang, Yanpei.,...&Sun, Zhe.(2024).S-Shaped Helical Singlet Diradicaloid and Its Transformation to Circumchrysene via a Two-Stage Cyclization.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(15).

Hu, Jinlian,et al."S-Shaped Helical Singlet Diradicaloid and Its Transformation to Circumchrysene via a Two-Stage Cyclization".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.15(2024).