Structural, photophysical, electrochemical and spintronic study of first-row metal Tetrakis(meso-triphenylamine)-porphyrin complexes: A combined experimental and theoretical study

• Published in: Dyes and pigments 2021-09, Vol.193, p.109469, Article 109469
• Main Authors: Sun, Ting, Zhang, Zilong, Xu, Jianbin, Liang, Lusheng, Mai, Chi-Lun, Ren, Lu, Zhou, Qin, Yu, Yaming, Zhang, Bao, Gao, Peng
• Format: Article
• Language: English
• Subjects: Meso-triphenylamine substituted; Metalloporphyrin; Photophysical and electrochemical properties; Single-crystal structure
• ISSN: 0143-7208; 1873-3743
• DOI: 10.1016/j.dyepig.2021.109469

Different metal ions in the center of 3d-metalloporphyrins have subtle influences on their structural, photophysical, electrochemical, and spintronic properties. A new series of symmetrically meso-substituted porphyrins with six first row transition metals, namely TPA-MPs (M = 2H, Mn, Fe, Co, Ni, Cu, and Zn) have been synthesized and characterized by various spectroscopic techniques. The electrostatic potential energy surface (ESP) calculated by density functional theory (DFT) exhibits the concentrated positive electrostatic potential on the substituted triphenylamine group, while the negative electrostatic potential localized on the porphyrin ring varies depending on metal ions. All compounds were crystallographically characterized and showed a coplanar porphyrin macrocyclic ring except for TPA-MnP and TPA-ZnP, which are distorted due to their occupied axial sites by Cl− and H2O, respectively. Furthermore, the X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) confirmed the valence states of the metal ions in the TPA-MPs. Electronic spectra revealed a gradual bathochromic shift following the order of TPA-CoP