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Metallopolymer Films Exhibiting Three-Color Electrochromism in the UV/Vis and Near-IR Region: Remarkable Utility of Trimetallic Clusters Bearing Thienyl Pendants and Their Mixed-Valent Charge Transfer Transitions

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Abstract

Novel oxo-centered, acetate-bridged trinuclear ruthenium clusters functionalized with two pyridine ligands with thienyl substituents, [Ru3O(CH3COO)6(CO)(L1)2] (1) and [Ru3O(CH3COO)6(CO)(L2)2] (2), where L1 = 4-(2-thienyl)pyridine and L2 = 4-(2,2′-bithienyl)pyridine, have been synthesized and characterized. The molecular structure of 2 has been determined by single-crystal X-ray diffraction. One-electron oxidation of 2 with silver(I) cation has led to the isolation of a CO-dissociated product, [Ru3O(CH3COO)6(H2O)(L2)2]PF6 (3·PF 6 ), and subsequent reaction with 4-dimethylaminopyridine (dmap) gave [Ru3O(CH3COO)6(dmap)(L2)2]PF6 (4·PF 6 ). Linear metallopolymers containing the {Ru3O(CH3COO)6} groups have been deposited onto indium-tin oxide surface via oxidative electropolymerization of 2, 3·PF 6 , and 4·PF 6 . These metallopolymer thin films exhibit three-color electrochromism in the UV/Vis and near-IR region associated with the Ru3 II,III,III, Ru3 III,III,III, and Ru3 III,III,IV oxidation states.

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Acknowledgments

This work was supported by Grants-in-Aid for Scientific Research on Innovative Areas “Coordination Programming” (No. 22108523) and “Molecular Activation” (No. 23105537), Grants-in-Aid for Scientific Research (A) (No. 21245016) and (B) (No. 20350029), Grant-in-Aid for Challenging Exploratory Research (No. 24655134), the Global COE Program “Science for Future Molecular Systems” from MEXT, and a grant from Kuraray Co., Ltd.–Kyushu University collaborative research. The NMR spectrometer and X-ray diffractometer used in this work are equipped in Center of Advanced Instrumental Analysis, Kyushu University. We also acknowledge Ms. Sakiko Taura (Kyushu University) for her assistance in obtaining AFM images.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Kyushu University, Nishi-ku, Fukuoka, 819-0395, Japan

    Rumiko Matsuse, Masaaki Abe, Yuki Tomiyasu, Atsushi Inatomi, Hiroaki Yonemura, Sunao Yamada & Yoshio Hisaeda

  2. International Research Center for Molecular Systems (IRCMS), Kyushu University, Nishi-ku, Fukuoka, 819-0395, Japan

    Yoshio Hisaeda

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  1. Rumiko Matsuse
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  2. Masaaki Abe
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Correspondence to Masaaki Abe or Yoshio Hisaeda.

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This paper is dedicated to Prof. Dr. Hiroshi Nishihara for his outstanding contribution to the field of metal-containing polymer.

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Matsuse, R., Abe, M., Tomiyasu, Y. et al. Metallopolymer Films Exhibiting Three-Color Electrochromism in the UV/Vis and Near-IR Region: Remarkable Utility of Trimetallic Clusters Bearing Thienyl Pendants and Their Mixed-Valent Charge Transfer Transitions. J Inorg Organomet Polym 23, 136–146 (2013). https://doi.org/10.1007/s10904-012-9758-9

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