A spectroscopic approach to identifying the out-of-plane conformations of Ni(II) meso-tetraphenylporphyrin in solution

doi:10.1016/j.molstruc.2022.133778

	A spectroscopic approach to identifying the out-of-plane conformations of Ni(II) meso-tetraphenylporphyrin in solution
	Wang, Shenhao 1,2; Huang, Qing 1,2
刊名	JOURNAL OF MOLECULAR STRUCTURE
	2022-12-05
卷号	1269
关键词	NiTPP Out-of-plane deformations DFT Molecular dynamics Raman spectroscopy 1 H-NMR
ISSN号	0022-2860
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.
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
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
内容类型	期刊论文
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).