Organic photoelectric materials have important applications in many fields. Through reasonable molecular design, the introduction of metal ions into organic molecules can effectively regulate the energy levels, energy gaps, and photoelectric properties of the materials in the front line, and have the opportunity to realize new functions that cannot be realized by simple organic materials.
In the past few years, the research team of Zhong Yuwu, a key laboratory of the Institute of Chemistry, Institute of Chemistry, Chinese Academy of Sciences, focused on design synthesis, electron transfer, thin film preparation and performance, near-infrared electrochromism, and information storage of multi-steady metal organic materials. Work was carried out in other areas (Figure 1). A series of bridged ring metal iridium complexes and triarylamine compounds with good redox activity were synthesized. Because the metal and bridging ligands are connected by carbon-metal bonds, the redox potential of the metal is significantly reduced and there is a strong electronic interaction between the redox centers. This kind of material has a multi-steady state property, and each state can be distinguished by the near-infrared absorption spectrum and the paramagnetic signal.
In the mixed-valence state, the material exhibits strong near-infrared absorption of charge-to-charge transfer. The electropolymerized films of the corresponding compounds show good near-infrared electrochromism, and have low operating voltages, long memory times, high contrast ratios, and short response times (Coord.Chem.Rev.2013, 257, 1357; Chem. (Sci. 2014, 5, 932; Chem. Sci. 2015, 6, 1308). With carboxyl groups as anchor groups, self-assembled monolayers of corresponding complexes can be prepared on the surface of ITO electrodes, and molecular-level near-infrared electrochromic and flip-flop storage functions can be successfully achieved (J.Am.Chem.) .Soc.2015,137,4058).
Recently, under the support of the National Natural Science Foundation of China, the Ministry of Science and Technology, and the Chinese Academy of Sciences, researchers designed and synthesized novel triarylamine bridged bis-guanidinium metal complexes and confirmed the molecular structure of the complexes through single crystal diffraction (Figure 2). These compounds have a three-step, single-electron reversible redox process at lower potential (+0.21, +0.44, +1.03 VvsAg/AgCl), ie, they have four stable reversible redox states, and each state has a characteristic near-infrared absorb. After the vinyl group is attached to the terminal ligand, a polymer film of the corresponding complex is prepared on the surface of the ITO electrode by electrochemical reduction polymerization. The film thickness can be controlled (10~200nm), the adhesion is good, and the coordination environment is completely preserved. The film has multiple steps of near-infrared electrochromism. In addition, the researchers to +0.35V, +0.75V and +1.30V voltage as input signal (In1, In2, In3), with the characteristics of the corresponding three redox state absorption as an output signal (Out3@1680nm; Out2@1170nm; Out1@750nm) realizes flip-flap-flop polymorphic information storage in film state (Angew.Chem.Int.Ed.2015, 54, 9192).
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