The geometry and electronic structures of iron(II) complexes with porphyrin (FeP) and tetrabenzoporphyrin (FeTBP) in ground and low-lying excited electronic states are determined by DFT (PBE0/def2-TZVP) calculations and the complete active space self-consistent field (CASSCF) method, followed by the multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2) approach to determine the dynamic electron correlation. The minima on the potential energy surfaces (PESs) of the ground (³A_2g) and low-lying, high-spin (⁵A_1g) electronic states correspond to the planar structures of FeP and FeTBP with D_4h symmetry. According to the results of the MCQDPT2 calculations, the wave functions of the ³A_2g and ⁵A_1g electronic states are single determinant. The electronic absorption (UV–Vis) spectra of FeP and FeTBP are simulated within the framework of the simplified time-dependent density functional theory (sTDDFT) approach with the use of the long-range corrected CAM-B3LYP function. The most intensive bands of the UV–Vis spectra of FeP and FeTBP occur in the Soret near-UV region of 370–390 nm.

As a follow-up to our study on aggregation of metal-etioporphyrin complexes (Colloids Surf. A. Physicochem. Eng. Asp. 2022, 648, 129284), we considered thin films of three isomers of copper(II) etioporphyrin deposited on hot substrates. Despite the almost identical absorption spectra of isomers, their solid-state superstructures differ remarkably both in form and size. The lateral conductivity of films is much less sensitive to an isomer-type, regardless of the substrate temperature. However, the dark conductivity of cold-grown films is about two orders of magnitude higher than that of hot-grown films, whereas the photoconductivity of the latter is 100–1700 times greater, depending on the isomer.