It is important to identify non-planar deformations of porphyrin macrocycle in metallo-porphyrin proteins due to their functional relevance. The relationship between non-planar deformations of porphyrin macrocycle and low frequency Raman spectral bands of Ni(II) meso-tetraphenyl porphyrin (NiTPP), with different coordination numbers, was studied by density functional theory (DFT), normal coordinate structural decomposition method and Raman experiments. The results show that the crystal of four-coordinate NiTPP has two major kinds of non-planar deformations: ruffling and saddling. The non-planar deformations of ruffling and saddling for NiTPP are 1.473 Å and 0.493 Å determined by DFT calculation. The ruffling and saddling deformations can be identified by using the low frequency Raman characteristic peaks (γ12, γ13) and (γ16, γ17), respectively. When four-coordinate NiTPP is transformed to the six-coordinate bis(pyrrolidine) NiTPP (NiTPP(Pyr)2), the large non-planar distortion of the porphyrin macrocycle almost disappears, with the non-planar deformation of saddling only about 0.213 Å estimated by DFT calculation. Experimentally, we can make use of the characteristic peaks of low frequency Raman spectra to identify the saddling deformation beyond 0.25 Å.
Skip Nav Destination
Article navigation
February 2023
Research Article|
February 01 2023
Use of low frequency Raman bands to identify non-planar deformation of Ni(II) meso-tetraphenylporphyrin induced by axial ligands
Special Collection:
Virtual Issue on Molecular Spectroscopy (2023)
Shen-hao Wang;
Shen-hao Wang
a
CAS Key Laboratory of High Magnetic Field and Ion Beam Physical Biology, Hefei Institutes of Physical Science, Institute of Intelligent Machines, Chinese Academy of Sciences
, Hefei 230031, China
b
Science Island Branch of Graduate School, University of Science and Technology of China
, Hefei 230026, China
Search for other works by this author on:
Muhammad Muhammad;
Muhammad Muhammad
a
CAS Key Laboratory of High Magnetic Field and Ion Beam Physical Biology, Hefei Institutes of Physical Science, Institute of Intelligent Machines, Chinese Academy of Sciences
, Hefei 230031, China
b
Science Island Branch of Graduate School, University of Science and Technology of China
, Hefei 230026, China
Search for other works by this author on:
Qing Huang
Qing Huang
*
a
CAS Key Laboratory of High Magnetic Field and Ion Beam Physical Biology, Hefei Institutes of Physical Science, Institute of Intelligent Machines, Chinese Academy of Sciences
, Hefei 230031, China
b
Science Island Branch of Graduate School, University of Science and Technology of China
, Hefei 230026, China
*Author to whom correspondence should be addressed. E-mail: [email protected]
Search for other works by this author on:
*Author to whom correspondence should be addressed. E-mail: [email protected]
Chin. J. Chem. Phys. 36, 57–65 (2023)
Article history
Received:
March 17 2021
Accepted:
April 21 2021
Citation
Shen-hao Wang, Muhammad Muhammad, Qing Huang; Use of low frequency Raman bands to identify non-planar deformation of Ni(II) meso-tetraphenylporphyrin induced by axial ligands. Chin. J. Chem. Phys. 1 February 2023; 36 (1): 57–65. https://doi.org/10.1063/1674-0068/cjcp2103049
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
Understanding photolysis of CH3ONO2 with on-the-fly nonadiabatic dynamics simulation at the ADC(2) level
Juanjuan Zhang, Jiawei Peng, et al.
Mechanistic insights into intramolecular energy transfer dynamics in photosensitizers for triplet-triplet annihilation upconversion
Tingting Fu, Yaxiong Wei, et al.
Review and perspective of single-molecule spectroscopy for
chemistry
Mingyi Xie, Yuxi Tian
Related Content
Room temperature magnetism of ordered porphyrin layers on Fe
Appl. Phys. Lett. (August 2019)
Electronic structure and optical properties of metal doped tetraphenylporphyrins
AIP Conference Proceedings (May 2018)
Time‐resolved and static optical properties of vibrationally excited porphyrins
J. Chem. Phys. (May 1991)
Femtosecond electronic relaxation of excited metalloporphyrins in the gas phase
J. Chem. Phys. (March 2006)