Reversible Electrochromic/Electrofluorochromic Dual Switching in Zn(II)-Based Metallo-Supramolecular Polymer FilmsClick to copy article linkArticle link copied!
- Sanjoy MondalSanjoy MondalElectronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, JapanMore by Sanjoy Mondal
- Dines Chandra SantraDines Chandra SantraElectronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, JapanMore by Dines Chandra Santra
- Susmita RoySusmita RoyElectronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, JapanMore by Susmita Roy
- Yemineni S. L. V. NarayanaYemineni S. L. V. NarayanaElectronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, JapanMore by Yemineni S. L. V. Narayana
- Takefumi YoshidaTakefumi YoshidaElectronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, JapanMore by Takefumi Yoshida
- Yoshikazu NinomiyaYoshikazu NinomiyaElectronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, JapanMore by Yoshikazu Ninomiya
- Masayoshi Higuchi*Masayoshi Higuchi*Email: [email protected]Electronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, JapanMore by Masayoshi Higuchi
Abstract
The introduction of novel materials with multifunctional chromogenic properties, such as electrochromic/electrofluorochromic (EC/EFC) properties, has recently attracted prospective interest in the development of various optoelectronic devices and smart windows. In this study, a novel Zn(II)-based metallo-supramolecular polymer (polyZn) has been developed as an ON/OFF switchable EFC application with prominent EC behavior. In this regard, the polymeric chain of polyZn was first synthesized by 1:1 complexation in a zigzag manner with Zn(II) ions at the metal center and 4,4′-[bis(2,2′:6′,2″-terpyridinyl)benzene]triphenylamine (LTPY-TPA) as the redox-active ditopic ligand. The polyZn exhibits excellent solubility in organic solvents and can form a very good uniform thin film on an indium tin oxide/glass substrate by spin-coating. In a neutral state, transparent polyZn exhibits a bright yellow color to the naked eye (absorption at ∼325 nm). The electroactive triphenylamine (TPA) core of LTPA-TPY, however, undergoes reversible single-electron oxidation when a positive bias of +1.6 V vs Ag/Ag+ is applied, generating radical cations (TPA ↔ TPA•+) with a significant drop in transparency (77%). A noticeable chromic shift in the hue of the film from brilliant yellow to green was observed with the appearance of a near-infrared absorption band at ∼897 nm with a tail of 1300–1600 nm. Interestingly, in addition to this EC phenomenon, the fabricated solid-state polyZn film exhibits intense, high-contrast reddish-orange photoluminescence with λem = 650 nm, which is significantly desired as a molecular probe for bioimaging. Both the TPA core and the redox-inactive Zn(II)-terpyridine core emit orange-red photoluminescence in polyZn, which is significantly quenched upon the oxidation of the film and is re-emitted at 0.0 V vs Ag/Ag+. This ON/OFF EFC transition was sustained for several cycles. This study should motivate to design and create distinctive new unique materials with combined EC/EFC behavior for the fabrication of optoelectronic devices by combining a metal-fluorescent core with a redox-active spacer.
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