Photophysical, electrochemical and electrochromic behavior of transition metal complexes with 1,10-phenanthroline ligands

Abstract

A series of non-noble transition metal complexes were synthesized by coordinating Fe2+, Co2+, and Ni2+ with ligands having a parent structure of 4,7-diphenyl-1,10-phenanthroline (L1 and L2) and dipyrido[3,2-a:2′,3′-c]phenazine (L3–L5), and their photophysical, electrochemical, and electrochromic properties were studied. Both transition metal ions and ligands produce more or less influence on these properties. Electrochromic properties such as color, optical contrast, response time, coloration efficiency and switching stabilities can be tuned by selecting proper metal ions, parent structure of ligands, and substituent groups. Theory calculation results indicate that electrons flow from the metallic center to the ligands. The UV–vis spectra of all five Fe(II) complexes showed a broad and strong MLCT band at ca. 530 nm. The UV–vis spectra of Fe(II), Co(II) and Ni(II) complexes with L2 ligand showed a strong LC (π–π*) band at ca. 325 nm. Electrochromic process caused a change in the intensity of LC and MLCT absorption. The ligands produced little effect on the bleached and colored states of Fe(II) complexes, all of them showed a bleached state of red and a colored state of purple-red probably due to the reversible Fe(II)/Fe(III) transition. Both Co(II) and Ni(II) complexes showed a bleached state of pale yellow, however, the ligands produced significant effect on their colored states probably due to the partially electron density displacement between the metal ions and the ligands. When the parent structure of ligand is 4,7-diphenyl-1,10-phenanthroline, electron-donating substituent such as –OCH3 is beneficial to electrochromic properties, and Fe(II) complexes have higher optical contrast and coloration efficiency compared to Co(II) and Ni(II) complexes. When the parent structure of ligand is dipyrido[3,2-a:2′,3′-c]phenazine, –CN substituent markedly enhances the optical contrast and coloration efficiency of Fe(II), Co(II) and Ni(II) complexes.