Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids
文献类型：期刊论文
| 作者 | Ke, Xian-Sheng1; Zhao, Hongmei2; Zou, Xiaoran2; Ning, Yingying1; Cheng, Xin1; Su, Hongmei2,3; Zhang, Jun-Long1,4 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2015-08-26 |
| 卷号 | 137期号:33页码:10745-10752 |
| 英文摘要 | Learning nature's approach to modulate photophysical properties of NIR porphyrinoids by fine-tuning beta-substituents including the number and position, in a manner similar to naturally occurring chlorophylls, has the potential to circumvent the disadvantages of traditional "extended pi-conjugation" strategy such as stability, molecular size, solubility, and undesirable pi-pi stacking. Here we show that such subtle structural changes in Pt(II) or Pd(II) cis/trans-porphodilactones (termed by cis/trans-Pt/Pd) influence photophysical properties of the lowest triplet excited states including phosphorescence, Stokes shifts, and even photosensitization ability in triplet triplet annihilation reactions with rubrene. Prominently, the overall upconversion capability (eta, eta = epsilon.Phi(UC)) of Pd or Pt trans-complex is 10(4) times higher than that of cis-analogue. Nanosecond time-resolved infrared (TR-IR) spectroscopy experiments showed larger frequency shift of nu(C=O) bands (ca. 10 cm(-1)) of cis-complexes than those of trans-complexes in the triplet excited states. These spectral features, combining with TD-DFT calculations, suggest the strong electronic coupling between the lactone moieties and the main porphyrin chromophores and thus the importance of precisely positioning beta-substituents by mimicking chlorophylls, as an alternative to "extended pi-conjugation", in designing NIR active porphyrinoids. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 公开日期 | 2015-10-27 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/27684]  |
| 专题 | 化学研究所_分子反应动力学实验室 |
| 作者单位 | 1.Peking Univ, Coll Chem & Mol Engn, State Key Lab Rare Earth Mat Chem & Applicat, Beijing Natl Lab Mol Sci, Beijing 100871, Peoples R China 2.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China 3.Beijing Normal Univ, Coll Chem, Beijing 100875, Peoples R China 4.Nanjing Univ, State Key Lab Coordinat Chem, Nanjing 210093, Jiangsu, Peoples R China |
| 推荐引用方式 GB/T 7714 | Ke, Xian-Sheng,Zhao, Hongmei,Zou, Xiaoran,et al. Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2015,137(33):10745-10752. |
| APA | Ke, Xian-Sheng.,Zhao, Hongmei.,Zou, Xiaoran.,Ning, Yingying.,Cheng, Xin.,...&Zhang, Jun-Long.(2015).Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,137(33),10745-10752. |
| MLA | Ke, Xian-Sheng,et al."Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 137.33(2015):10745-10752. |
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来源：化学研究所
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