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Assessment of the performance of six indices in predicating the aromaticity of planar porphyrinoids

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Abstract

Context and results

Aromaticity is a fundamental chemical concept that has been widely used in explaining the reactivity, stability, structure, and magnetic properties of many molecules such as conjugated macrocycles, metal heterocyclic compounds, and certain metal clusters. Porphyrinoids (including porphyrin) are of particular interest in terms of diverse aromaticity. Various indices therefore have been used to predict the aromaticity of porphyrin-like macrocycles. However, the reliability of these indices for porphyinoids is always questionable. In order to assess the performance of the indices, we have selected six representative indices to predict the aromaticity of 35 porphyrinoids. The calculated values were then compared with the corresponding results obtained from experiments. Our studies suggest that the theoretical prediction by nucleus independent chemical shifts (NICS), topology of the induced magnetic field (TIMF), anisotropy of the induced current density (AICD), and gauge including magnetically induced current method (GIMIC) are essentially consistent with experimental evidence in all 35 cases and thus are preferred indices.

Computational and theoretical techniques

Based on density functional theory, the performance of the NICS, TIMF, AICD, GIMIC, harmonic oscillator model of aromaticity (HOMA), and multicenter bond order (MCBO) indices were evaluated theoretically. Molecular geometries were optimized at the M06-2X/6-311G** level. NMR calculations using GIAO or CGST method were performed at the M06-2X/6-311G** level. The above calculations were carried out using Gaussian16 suite. The TIMF, GIMIC, HOMA, and MCBO indices were obtained using the Multiwfn program. The AICD outputs were visualized using the POV-Ray software.

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Data Availability

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Acknowledgements

We thank the high-performance computing center, Tongji Medical College of Huazhong University of Science and Technology, for providing computing resources.

Funding

The authors received financial support from the National Natural Science Foundation of China (22171289 and 21672141 to Z. Z. and 21273089 to X. C.)

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Authors and Affiliations

  1. Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South-Central Minzu University, Wuhan, 430074, China

    Wenjing Ding, Zhan Zhang & Xi Chen

  2. College of Pharmacy, University of Kentucky, Lexington, KY, 40536, USA

    Chang-guo Zhan

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  1. Wenjing Ding
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Contributions

Wenjing Ding performed computation and prepared the manuscript. Zhan Zhang and Xi Chen analyzed the data and revised manuscript. Chang-guo Zhan checked the computational results and made important suggestions.

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Correspondence to Zhan Zhang or Xi Chen.

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Ding, W., Zhang, Z., Chen, X. et al. Assessment of the performance of six indices in predicating the aromaticity of planar porphyrinoids. J Mol Model 29, 83 (2023). https://doi.org/10.1007/s00894-023-05485-9

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