Relevance of the DFT method to study expanded porphyrins with different topologies

• Published in: Journal of computational chemistry Vol. 38; no. 32; pp. 2819 - 2828
• Main Authors: Torrent‐Sucarrat, Miquel, Navarro, Sara, Cossío, Fernando P., Anglada, Josep M., Luis, Josep M.
• Format: Journal Article
• Language: English
• Published: United States Wiley Subscription Services, Inc 15.12.2017
• Subjects: Aromatic compounds; aromaticity; Density functional theory; density functional theory methods; Dispersion; DLPNO‐CCSD(T); expanded porphyrin; Hückel; Mathematical analysis; Möbius; Porphyrins; Potential energy; spurious stationary points; Switches; Topology; expanded porphyrin; density functional theory methods; Möbius; DLPNO-CCSD(T); spurious stationary points; Hückel; aromaticity
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.25074

Meso‐aryl expanded porphyrins present a structural versatility that allows them to achieve different topologies with distinct aromaticities. Several studies appeared in the literature studying these topological switches from an experimental and theoretical point of view. Most of these publications include density functional theory calculations, being the B3LYP the most used methodology. In this work, we show that the selection of the functional has a critical role on the geometric, energetic, and magnetic results of these expanded porphyrins, and that the use of an inadequate methodology can even generate spurious stationary points on the potential energy surface. To illustrate these aspects, in this article we have studied different molecular distortions of two expanded porphyrins, [32]‐heptaphyrin and [26]‐hexaphyrin using 11 DFT functionals and performing single point energy calculations at the local pair natural orbital coupled cluster DLPNO‐CCSD(T) method, which have been carried out for benchmarking purposes. For some selected functionals, the dispersion effects have also been evaluated using the D3‐Grimme's dispersion correction with Becke–Johnson damping. Our results let us to conclude that the CAM‐B3LYP, M05‐2X, and M06‐2X functionals are the methodologies that provide a more consistent description of these topological switches, while other methods, such as B3LYP, BPE, and BP86, show a biased description. © 2017 Wiley Periodicals, Inc. The selection of the density functional method has a critical role on the geometric, energetic, and magnetic results of the expanded porphyrins. As illustrative examples, we study two challenging distortions using 11 dispersion‐corrected and –uncorrected DFT functionals and performing DLPNO‐CCSD(T) single‐point calculations for benchmarking purposes. The methodologies that present the worst description of these topological distortions are the B3LYP, PBE, BP86, WB97XD, and TPSSh functionals. B3LYP is the most used functional in previous studies of the Hückel–Möbius conformational switches. An intermediate performance is obtained from the BMK, M06L, and BH&HLYP methods. The methodologies that show a more consistent behavior with respect to the DLPNO‐CCSD(T) results are the CAM‐B3LYP, M05‐2X, and M06‐2X functionals.