Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast Electrochromism
This study is dedicated to the design of multiple redox-active oligonuclear manganese complexes supported with a bis(tetradentate) ligand (TPDP = 1,3-bis(bis(2-pyridinylmethyl)amino)-2-propanol) for high-contrast electrochromism based on the reversible redox process between Mn(II) (colorless) and Mn...
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2025-05-01
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| author | Yi-Ting Wu Hao-Tian Deng Li-Yi Zhang Meng-Die Li Feng-Rong Dai Zhong-Ning Chen |
| author_facet | Yi-Ting Wu Hao-Tian Deng Li-Yi Zhang Meng-Die Li Feng-Rong Dai Zhong-Ning Chen |
| author_sort | Yi-Ting Wu |
| collection | DOAJ |
| description | This study is dedicated to the design of multiple redox-active oligonuclear manganese complexes supported with a bis(tetradentate) ligand (TPDP = 1,3-bis(bis(2-pyridinylmethyl)amino)-2-propanol) for high-contrast electrochromism based on the reversible redox process between Mn(II) (colorless) and Mn(III) (dark brown). Pentanuclear Mn<sub>5</sub> complex <b>1</b> (colorless) was synthesized via a one-pot reaction of Mn<sup>2+</sup> and TPDP, while tetranuclear Mn<sub>4</sub> complex <b>2</b> (brown) was obtained through aerial oxidation of complex <b>1</b>. Mn<sub>5</sub> complex <b>1</b> features a central MnCl<sub>6</sub> unit connected to two Mn<sub>2</sub>(<i>μ</i>-TPDP) fragments through <i>μ</i><sub>3</sub>-Cl<sup>−</sup> and <i>μ</i>-Cl<sup>−</sup>, whereas Mn<sub>4</sub> complex <b>2</b> adopts a symmetric tetranuclear structure with two mixed-valence Mn<sub>2</sub><sup>II,III</sup>(<i>μ</i>-TPDP)(<i>μ</i>-Cl) fragments that are further linked by <i>μ</i>-oxo. Electrochemical studies revealed multi-step reversible redox properties for both complexes, attributed to Mn<sup>II</sup>/Mn<sup>III</sup> processes with significant electronic coupling (Δ<i>E</i><sub>1/2</sub> = 0.27–0.37 V) between Mn centers. Spectroelectrochemical analysis revealed dynamic optical modulation through the tunable d-d transition and ligand-to-metal charge transfer (LMCT) state through reversible multiple redox processes based on Mn(II) ⇆ Mn(III) interconversion. The fabricated electrochromic device (ECD) exhibited reversible and high optical contrast between the colored state (dark brown) and the bleaching state (colorless). The results highlight the potential of polynuclear manganese complexes as high-contrast electrochromic materials for next-generation smart windows and adaptive optical technologies. |
| format | Article |
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| publishDate | 2025-05-01 |
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| spelling | doaj-art-4a2e4df9ff1742e885c42471faffef962025-08-20T02:31:12ZengMDPI AGMolecules1420-30492025-05-01309205410.3390/molecules30092054Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast ElectrochromismYi-Ting Wu0Hao-Tian Deng1Li-Yi Zhang2Meng-Die Li3Feng-Rong Dai4Zhong-Ning Chen5State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaThis study is dedicated to the design of multiple redox-active oligonuclear manganese complexes supported with a bis(tetradentate) ligand (TPDP = 1,3-bis(bis(2-pyridinylmethyl)amino)-2-propanol) for high-contrast electrochromism based on the reversible redox process between Mn(II) (colorless) and Mn(III) (dark brown). Pentanuclear Mn<sub>5</sub> complex <b>1</b> (colorless) was synthesized via a one-pot reaction of Mn<sup>2+</sup> and TPDP, while tetranuclear Mn<sub>4</sub> complex <b>2</b> (brown) was obtained through aerial oxidation of complex <b>1</b>. Mn<sub>5</sub> complex <b>1</b> features a central MnCl<sub>6</sub> unit connected to two Mn<sub>2</sub>(<i>μ</i>-TPDP) fragments through <i>μ</i><sub>3</sub>-Cl<sup>−</sup> and <i>μ</i>-Cl<sup>−</sup>, whereas Mn<sub>4</sub> complex <b>2</b> adopts a symmetric tetranuclear structure with two mixed-valence Mn<sub>2</sub><sup>II,III</sup>(<i>μ</i>-TPDP)(<i>μ</i>-Cl) fragments that are further linked by <i>μ</i>-oxo. Electrochemical studies revealed multi-step reversible redox properties for both complexes, attributed to Mn<sup>II</sup>/Mn<sup>III</sup> processes with significant electronic coupling (Δ<i>E</i><sub>1/2</sub> = 0.27–0.37 V) between Mn centers. Spectroelectrochemical analysis revealed dynamic optical modulation through the tunable d-d transition and ligand-to-metal charge transfer (LMCT) state through reversible multiple redox processes based on Mn(II) ⇆ Mn(III) interconversion. The fabricated electrochromic device (ECD) exhibited reversible and high optical contrast between the colored state (dark brown) and the bleaching state (colorless). The results highlight the potential of polynuclear manganese complexes as high-contrast electrochromic materials for next-generation smart windows and adaptive optical technologies.https://www.mdpi.com/1420-3049/30/9/2054manganese complexesmixed-valent compoundsredoxelectrochromismelectrochromic device |
| spellingShingle | Yi-Ting Wu Hao-Tian Deng Li-Yi Zhang Meng-Die Li Feng-Rong Dai Zhong-Ning Chen Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast Electrochromism Molecules manganese complexes mixed-valent compounds redox electrochromism electrochromic device |
| title | Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast Electrochromism |
| title_full | Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast Electrochromism |
| title_fullStr | Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast Electrochromism |
| title_full_unstemmed | Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast Electrochromism |
| title_short | Oligonuclear Manganese Complexes with Multiple Redox Properties for High-Contrast Electrochromism |
| title_sort | oligonuclear manganese complexes with multiple redox properties for high contrast electrochromism |
| topic | manganese complexes mixed-valent compounds redox electrochromism electrochromic device |
| url | https://www.mdpi.com/1420-3049/30/9/2054 |
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