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

Matsuse, Rumiko; Abe, Masaaki; Tomiyasu, Yuki; Inatomi, Atsushi; Yonemura, Hiroaki; Yamada, S.; Hisaeda, Yoshio

doi:10.1007/s10904-012-9758-9

Cited by 11 publications

(8 citation statements)

References 47 publications

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“…In another paper, Toma et al [7] demonstrated a very stable electrochromic device based on triruthenium clusters adsorbed on nanocrystalline titanium dioxide films. Recently, Matsuse et al [8] presented a new device based on triruthenium cluster metallopolymers that displays threecolor electrochromism associated with the [Ru 3 couple (monitored at 923 nm) and 80 % conversion.…”

Section: Introductionmentioning

confidence: 99%

“…The resolution of the absorption measurement is 0.5 s, and the switching process takes 1 s to convert Ͼ90 % of the absorbance, which is much faster than analogous films of polymeric complexes reported in the literature. [8] In addition, the film is quite stable: the absorbance loss is negligible over 30 min and hundreds of cycles. This outcome is attributed to the hydrophobic character of the phenylazopyridine ligand, which prevents lixiviation of the film into the aqueous solution and strongly binds to the triruthenium cluster.…”

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confidence: 99%

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Ruthenium Acetate Cluster Amphiphiles and Their Langmuir–Blodgett Films for Electrochromic Switching Devices

et al. 2014

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We synthesized a long-chain phenylazopyridine ligand and used it to obtain three new amphiphilic trinuclear ruthenium acetate clusters. The amphiphilicity and anisometric form of the long-chain ligand allowed the complexes to selfassemble at the liquid-air interface and enabled their deposition by the Langmuir-Blodgett technique. We obtained the linear complex [Ru 3 O(C 2 H 3 O 2 ) 6 (py) 2 L] + [L = 4-(4-dodecyl-

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Ruthenium Acetate Cluster Amphiphiles and Their Langmuir–Blodgett Films for Electrochromic Switching Devices

et al. 2014

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“…42 For electrochromic devices, triruthenium thin films were prepared on ITO-coated glass substrates via electropolymerization. 43 Three distinct Ru 3 redox states, (II, III, III), (III, III, III), and (III, III, IV), are reversibly switched by an external potential and exhibit visible and NIR color changes. The electrochromic operation was performed repeatedly without degradation, and the on/off NIR absorption could be useful for security devices and heat-shielding purposes.…”

Section: Covalently-bonded and Supramolecular MV Assembliesmentioning

confidence: 99%

Stimuli-responsive Mixed-valence Architectures: Synthetic Design and Interplay between Mobile and Introduced Charges

Tahara

Abe

2020

Chem. Lett.

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in 2015. His current research focuses on 2D/3D functional molecular architectures derived from coordination compounds. Keishiro Tahara received Ph.D. from Kyushu University under the guidance of Prof. Y. Hisaeda in 2011. Then he joined to the group of Prof. J. Kikuchi in Nara Institute of Science and Technology as a postdoctoral researcher, and became an assistant professor in 2011. Then he moved to the group of Prof. M. Abe in University of Hyogo in 2016 and has been an assistant professor. His research interests are fabrication of redox-active molecular materials.

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“…In addition to the interesting applications mentioned above, electrochromism has been studied using electropolymerized conducting metallopolymers. Cyclometalated platinum(II) chloride bound to a 4-(diphenylamino)phenyl group ( 1 ) and ruthenium(II) complexes with N–N bidentate ligands functionalized with vinyl ( 2 − 5 ) or thiophene groups ( 6a – 6c ) − have been electropolymerized, and their near-infrared electrochromic properties have been studied (Figure ). N -heterocyclic carbene (NHC)-based metallopolymers containing iridium ( 7a ), gold ( 7b ), copper ( 8a ), or silver ( 7c , 8b ) metal centers with thiophene groups have also been investigated for the visible electrochromism properties they display. , An Fe(II) complex with N -(pyridin-2-ylmethylidene)-2,5-bis(thiophen-2-yl)aniline ligand ( 9 ) was prepared to build a conducting electrochromic metallopolymer film with a color change from orange to black under applied potential (0.6 V vs Ag) .…”

Section: Introductionmentioning

confidence: 99%

A Thiophene-Containing Conductive Metallopolymer Using an Fe(II) Bis(terpyridine) Core for Electrochromic Materials

Liang

Strohecker

Lynch

et al. 2016

ACS Appl. Mater. Interfaces

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Three Fe(II) bis(terpyridine)-based complexes with thiophene (Fe(L1)), bithiophene (Fe(L2)), and 3,4-ethylenedioxythiophene (Fe(L3)) side chains were designed and synthesized for the purpose of providing two terminal active sites for electrochemical polymerization. The corresponding metallopolymers (poly-Fe(Ln), n = 2 or 3) were synthesized on indium tin oxide (ITO)-coated glass substrates via oxidative electropolymerization of the thiophene-substituted monomers and characterized using electrochemistry, X-ray photoelectron spectroscopy, UV-vis spectroscopy, and atomic force microscopy. The film poly-Fe(L2) was further studied for electrochromic (EC) color-switching properties and fabricated into a solid-state EC device. Poly-Fe(L2) films exhibit an intense MLCT absorption band at 596 nm (ε = 4.7 × 10 M cm) in the UV-vis spectra without any applied voltage. Upon application of low potentials (between 1.1 and 0.4 V vs Fc/Fc), the obtained electropolymerized film exhibited great contrast with a change of transmittance percentage (ΔT%) of 40% and a high coloration efficiency of 3823 cm C with a switching time of 1 s. The film demonstrates commonplace stability and reversibility with a 10% loss in peak current intensity after 200 cyclic voltammetry cycles and almost no loss in change of transmittance (ΔT%) after 900 potential switches between 1.1 and 0.4 V (vs Fc/Fc) with a time interval of 0.75 s. The electropolymerization of Fe(L2) provides convenient and controllable film fabrication. Electrochromic behavior was also achieved in a solid-state device composed of a poly-Fe(L2) film and a polymer-supported electrolyte sandwiched between two ITO-coated glass electrodes.

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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

Cited by 11 publications

References 47 publications

Ruthenium Acetate Cluster Amphiphiles and Their Langmuir–Blodgett Films for Electrochromic Switching Devices

Ruthenium Acetate Cluster Amphiphiles and Their Langmuir–Blodgett Films for Electrochromic Switching Devices

Stimuli-responsive Mixed-valence Architectures: Synthetic Design and Interplay between Mobile and Introduced Charges

A Thiophene-Containing Conductive Metallopolymer Using an Fe(II) Bis(terpyridine) Core for Electrochromic Materials

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