Benchmarking computational methods and influence of guest conformation on chirogenesis in zinc porphyrin complexes

Abstract

Different computational methods and influence of the guest conformation and solvent effect to analyze chirogenesis in zinc porphyrins by several chiral compounds have been investigated.

Chirogenesis in Zinc Porphyrins: Theoretical Evaluation of Electronic Transitions, Controlling Structural Factors and Axial Ligation

“…For zinc porphyrins the ligation causes a red shift [91,92,153] . In addition, upon axial ligation the B electronic transitions acquire a charge transfer character [41,99] …”

“…The simulations were done using the ωB97X‐D [172] functional, which previously showed a good agreement with the experimental spectra of zinc porphyrins, [98,99,166] and using the cc‐pVTZ [173–177] and aug‐cc‐pVDZ [173,174,178] basis sets. The cc‐pVTZ basis set was chosen, since its quality was enough for adequate description of the corresponding electric dipole moments and therefore rotatory strengths [99,179–181] . In addition to this basis set, a smaller basis set with diffused functions – aug‐cc‐pVDZ was tried, since in some works it was stated that the diffused functions are essential for ECD spectral simulations [180–183] .…”

“…In addition to this basis set, a smaller basis set with diffused functions – aug‐cc‐pVDZ was tried, since in some works it was stated that the diffused functions are essential for ECD spectral simulations [180–183] . Also, previous investigation showed that a good correlation between the simulated and experimental spectra can be obtained already with the DZVP basis set [99,137,184] . However, Nguyen et al [185] .…”

Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative

“…Computational details. Structural optimization was performed using resolution of identity (RI) approximation [48][49][50], PB86 functional [51,52] with D3 dispersion correction [53] and def2-SV(P) basis set [54] implemented in Turbomole 7.0 [55], which showed good agreement with experimental data [56][57][58], as in a gas phase and in solvent. To include solvent effect the COSMO solvent model [59] was used.…”

“…The UV-Vis and CD spectra were simulated using the Gaussian16 [61] software and TD-DFT method [62][63][64]. For spectra simulations, the ωB97X-D functional [65] and cc-pVDZ basis set [66][67][68] with the SMD solvent model [69] were used, since this level of theory showed good agreement with experimental data [56,57,70]. The first 10 excited states were calculated in order to ensure that the B band region of the spectrum was covered.…”