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Substituent effects on geometric and electronic properties of iron tetraphenylporphyrin: a DFT investigation

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Abstract

To investigate the effects of the substituents, substituent positions and axial chloride ligand on the geometric and electronic properties of the iron tetraphenylporphyrin (FeTPP), a series of the substituented iron tetraphenylporphyrins and their chlorides, FeT(o/p-R)PP and FeT(o/p-R)PPCl (R = −H, -Cl, -NO2, -OH, -OCH3), were systematically calculated without any symmetry constraint by using DFT method. For geometric structure, the substituent position and axial Cl ligand change the configuration of the iron porphyrin obviously. The ortho-substituents prefer making the phenyls perpendicular to the porphyrin ring; the axial chloride draws the central Fe ion ∼0.500 Å out of the porphyrin plane toward the ligand. With regard to electronic properties, it is found that ELUMO could be related to the catalytic activity. The electron-withdrawing group always lowers the energies of both frontier orbitals, while the electron-donating one heightens them simultaneously, but they affect the EHOMO and ELUMO in the same sequence, -NO2 < −Cl < −H < −OH < −OCH3. The substituent effects on the central Fe ion were explored by calculating NBO charge distribution, spin density and natural electron configuration.

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Acknowledgments

This work was supported by the State Key Program of National Natural Science of China (Grant No. 21036009), the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality (Grant No.PHR201107104 and PHR200907105) and the National Natural Science Foundation of China for the Youth (Grant No. 20903007).

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Authors and Affiliations

  1. Institute of Green Chemistry and Fine Chemicals, Beijing University of Technology, 100124, Beijing, China

    Lu Wei, Yuanbin She & Yanmin Yu

  2. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, 100190, Beijing, China

    Xiaoqian Yao & Suojiang Zhang

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  1. Lu Wei
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  2. Yuanbin She
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  3. Yanmin Yu
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Correspondence to Yuanbin She.

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Wei, L., She, Y., Yu, Y. et al. Substituent effects on geometric and electronic properties of iron tetraphenylporphyrin: a DFT investigation. J Mol Model 18, 2483–2491 (2012). https://doi.org/10.1007/s00894-011-1279-x

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