期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 44, 页码 15622-15632出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201501938
关键词
DFT calculations; electronic absorption spectroscopy; porphyrins; Raman spectroscopy; zinc
资金
- Australian Research Council Centre of Excellence Scheme [CE 140100012]
- Australian National Fabrication Facility
- MacDiarmid Institute (New Zealand)
A series of zinc porphyrins substituted at adjacent -positions with a CN group and para-substituted ethenyl/ethynyl-phenyl group have been studied using electronic absorption spectroscopy, resonance Raman spectroscopy and DFT calculations. The oxidative nucleophilic substitution of hydrogen was utilized for the introduction of a cyano substituent on the porphyrin ring. This modification has a remarkable electronic effect on the ring. The resulting porphyrin cyanoaldehyde was further modified in Wittig condensations to give series of arylalkene- and arylalkyne-substituted derivatives. This substitution pattern caused significant redshifting and broadening of the B band, tuning from 433-446nm. Additionally the Q/B band intensity ratios show much higher values than observed for the parent porphyrin ZnTPP (0.20 vs. 0.03). Careful analysis of the electronic transitions using DFT and resonance Raman spectroscopy reveal that the substituent does not significantly perturb the electronic structure of the porphyrin core, which is still well described by Gouterman's four-orbital model. However, the substituents do play a role in elongating the conjugation length and this results in the observed spectral changes.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据