A spectroscopic approach to identifying the out-of-plane conformations of Ni(II) meso-tetraphenylporphyrin in solution
文献类型：期刊论文
| 作者 | Wang, Shenhao1,2; Huang, Qing1,2
|
| 刊名 | JOURNAL OF MOLECULAR STRUCTURE
 |
| 出版日期 | 2022-12-05 |
| 卷号 | 1269 |
| ISSN号 | 0022-2860 |
| 关键词 | NiTPP Out-of-plane deformations DFT Molecular dynamics Raman spectroscopy 1 H-NMR |
| DOI | 10.1016/j.molstruc.2022.133778 |
| 通讯作者 | Huang, Qing(huangq@ipp.ac.cn) |
| 英文摘要 | Ni(II) meso-tetraphenylporphyrin (NiTPP) is a model molecule whose substituent causes out-of-plane (oop) deformations of the porphyrin macrocycle. Although the conformers of NiTPP in the solution had been tentatively explored, the determination of its specific conformers was controversial. In this work, based on the conformational search through molecular dynamics (MD), three energy lowest-lying con-formers of NiTPP were sorted out, namely, the S 4 (staggered) conformer, the C 2 (eclipsed) conformer, and the C 1 (eclipsed-staggered) conformer. According to the high-precision free energy calculation based on density functional theory (DFT), the Raman and 1H-NMR spectra of the three conformers were calcu-lated. The actual spectra of NiTPP in solution resulted from the sum spectra of the mixture conformers, so with the consideration of the corresponding conformation weights, the experimental spectra could be stimulated. Our results showed that only at the low-frequency similar to 215 cm -1, did the Raman spectrum in solution differ significantly from that in solid powder. On the other hand, the 1H-NMR spectra of the NiTPP conformers were remarkably different, and none of the single conformer's 1H-NMR range could match the experimental 1H-NMR spectrum. However, with the consideration of the existence of three dominant conformations, the observed 1H-NMR spectrum could be well simulated, confirming the ratio-nal mixture of the three dominant conformers existing in the aqueous solution. Therefore, this work has not only resolved the different conformers of NiTPP in solution, but also provided an effective approach to combining DFT, Raman, and 1H-NMR analytical tools for identifying different oop conformations of metalloporphyrins in solution.(c) 2022 Elsevier B.V. All rights reserved. |
| WOS关键词 | EXCITED-STATE DISPLACEMENTS ; NONPLANAR HEME DEFORMATIONS ; PORPHYRIN FORCE-FIELD ; RESONANCE RAMAN ; VIBRATIONAL-SPECTRA ; NICKEL PORPHINE ; SINGLE-MOLECULE ; CYTOCHROME-C ; BASIS-SETS ; DENSITY |
| 资助项目 | National Natural Science Foun-dation of China ; Research Integration Program of Hefei Institutes of Physical Science, Chinese Academy of Sciences ; [11635013] |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| 出版者 | ELSEVIER |
| WOS记录号 | WOS:000878184600007 |
| 资助机构 | National Natural Science Foun-dation of China ; Research Integration Program of Hefei Institutes of Physical Science, Chinese Academy of Sciences |
| 源URL | [http://ir.hfcas.ac.cn:8080/handle/334002/130029]  |
| 专题 | 中国科学院合肥物质科学研究院 |
| 通讯作者 | Huang, Qing |
| 作者单位 | 1.Chinese Acad Sci, Hefei Inst Phys Sci, Inst Intelligent Machines, Hefei Inst Intelligent Agr,CAS Key Lab High Magnet, Hefei, Peoples R China 2.Univ Sci & Technol China, Grad Sch, Sci Isl Branch, Hefei, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wang, Shenhao,Huang, Qing. A spectroscopic approach to identifying the out-of-plane conformations of Ni(II) meso-tetraphenylporphyrin in solution[J]. JOURNAL OF MOLECULAR STRUCTURE,2022,1269. |
| APA | Wang, Shenhao,&Huang, Qing.(2022).A spectroscopic approach to identifying the out-of-plane conformations of Ni(II) meso-tetraphenylporphyrin in solution.JOURNAL OF MOLECULAR STRUCTURE,1269. |
| MLA | Wang, Shenhao,et al."A spectroscopic approach to identifying the out-of-plane conformations of Ni(II) meso-tetraphenylporphyrin in solution".JOURNAL OF MOLECULAR STRUCTURE 1269(2022). |
入库方式： OAI收割
来源：合肥物质科学研究院
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