Spectrometric measurements and DFT studies on new complex of copper (II) with 2-((E)-9-ethyl-3-(2-(6-(4-methylpyridin-2-yl)pyridin-3-yl)vinyl)-9H-carbazole

Abstract

The molecular structure of a new complex of copper (II) with (E)-9-ethyl-3-(2-(6-(4-methylpyridin-2-yl)pyridin-3-yl)vinyl)-9H-carbazole ([Cu2(emppc)2Cl2]Cl2) was optimized with B3LYP/LanL2DZ, PBE1PBE/LanL2DZ and M062X/LanL2DZ theoretical level. The ligand, (E)-9-ethyl-3-(2-(6-(4-methylpyridin-2-yl)pyridin-3-yl)vinyl)-9H-carbazole (emppc), binds to Cu(II) ions with a bi-dentate mode, two Cl(-) serve as bridging ligand, each Cu(II) ion has a highly distorted tetrahedron coordination geometry. With M062X/LanL2DZ theoretical level, the calculated interaction energies of Cu(II) with coordination atoms N are between 183.3-200.0kJmol(-1) for α spin and 319.4-324.9kJmol(-1) for β spin, and interaction energies of Cu(II) with coordination atoms Cl atom are 248.0-252.4kJmol(-1) for α spin and 332.6-333.6kJmol(-1) for β spin. The experimental Fourier transform infrared spectrum was assigned. The calculated IR based on B3LYP/LanL2DZ, PBE1PBE/LanL2DZ and M062X/LanL2DZ methods were performed and compared with experimental results. The UV-Vis experimental spectra of [Cu2(emppc)2Cl2]Cl2 was measured in methanol solution. The calculated electronic spectrum was performed with TD/M062X and PCM-TD/M062X methods with LanL2DZ basis set. The nature bond orbital analysis and temperature dependence of the thermodynamic properties were calculated with the same methods.

l-Isoleucine-Schiff Base Copper(II) Coordination Polymers: Crystal Structure, Spectroscopic, Hirshfeld Surface, and DFT Analyses

“…This is mainly caused by harmonic approximation and the incomplete treatment of electron correlation in these calculations . To aid comparison between the predicted and observed frequencies, we employed the correction factor for the M06-2x functional with the LANL2DZ basis for high and low frequencies based on the report of Zhang and co-workers in 2016 . The resulting calculated vibrational spectra of the complex compared to the experimental one are presented in Figure S9.…”

“… 55 To aid comparison between the predicted and observed frequencies, we employed the correction factor for the M06-2x functional with the LANL2DZ basis for high and low frequencies based on the report of Zhang and co-workers in 2016. 56 The resulting calculated vibrational spectra of the complex compared to the experimental one are presented in Figure S9 . The summary of the vibrational frequencies and the assignment of their vibrational modes are shown in Tables S4 and S5 .…”

Design of new hole transport materials based on triphenylamine derivatives using different π-linkers for the application in perovskite solar cells. A theoretical study

“…In the present work, the molecular geometries of the triphenylamine derivatives were optimized by the functional M06-2X (54% HF exchange) (Zhao and Truhlar, 2008) with the 6-311++G(d,p) basis set (Hariharan and Pople, 1973;Frisch et al, 1984). The functional M06-2X was selected because this functional has shown the best agreement with experimental results of infrared spectrum in previous work with carbazole derivatives (Zhang et al, 2016). All calculated geometries are in the global minimum of their potential energy surface; this was confirmed with frequency calculations.…”