N-methyl-21-thiaporphyrins

Tejinder Kaur, Way-Zen Lee, Mangalampalli Ravikanth*

*此作品的通信作者

研究成果: 雜誌貢獻期刊論文同行評審

2 引文 斯高帕斯(Scopus)

摘要

We synthesized five N-methyl-meso-tetraaryl-21-thiaporphyrins in 55-60% yield by treating the appropriate meso-tetraaryl-21-thiaporphyrin with CH 3I. The N-methyl-21-thiaporphyrins were characterized by HRMS, 1D and 2D NMR spectroscopy, absorption spectroscopy, fluorescence spectroscopy, and electrochemical techniques, and the structure of one of the compounds was obtained by X-ray crystallography. 1D and 2D NMR spectroscopy were used to identify all of the resonances observed in the 1H NMR spectra of the N-methyl-21-thiaporphyrins. NMR studies indicated that the methylation occurred at the pyrrole ring that is opposite to the thiophene ring. In the 1H NMR spectra, the methylation resulted in significant upfield shifts of the pyrrole and thiophene protons; the maximum shifts were noted for the protons of the N-methylated pyrrole ring of the N-methyl-21-thiaporphyrins. The X-ray structure of one of the N-methyl-21-thiaporphyrins revealed significant deviation of the N-methylated pyrrole ring from the reference plane defined by the four meso carbon atoms, and the porphyrin ring is strongly distorted compared to the 21-thiaporphyrin ring. The absorption studies revealed that the N-methyl-21-thiaporphyrins showed four Q bands and one strong Soret band, which were bathochromically shifted compared to those of the 21-thiaporphyrins. The electrochemical studies on the N-methyl-21-thiaporphyrins indicated that the oxidation potentials became less positive and there were negligible shifts in the reduction potentials; the HOMO-LUMO energy gap decreased compared with that of the 21-thiaporphyrins. The N-methyl-21-thiaporphyrins are weakly fluorescent with low quantum yields and singlet-state lifetimes. The spectral and electrochemical studies indicated that N-methylation of the pyrrole ring of 21-thiaporphyrins significantly alters the electronic properties of the 21-thiaporphyrin macrocycle.

原文英語
頁(從 - 到)2261-2267
頁數7
期刊European Journal of Organic Chemistry
2014
發行號11
DOIs
出版狀態已發佈 - 2014 一月 1

ASJC Scopus subject areas

  • 物理與理論化學
  • 有機化學

指紋

深入研究「N-methyl-21-thiaporphyrins」主題。共同形成了獨特的指紋。

引用此