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 macrocyclic ring of expanded porphyrins presents a conformational versatility that leads to original structural motifs and generates unique Hückel-to-Möbius topological switches. These systems can act as optoelectronic materials and their range of applicability depends on the high values of the nonlinear optical properties (NLOP) and the large differences between the Hückel and Möbius structures. With the aim to design new topological switches with the optimum NLOP, we have performed a DFT computational study on the effect of three different geometric and electronic factors of the meso-substituents: i) their electron-withdrawing and -releasing character; ii) their distribution along
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