Iron Phthalocyanine Incorporated Metallo-Supramolecular Polymer for Superior Electrochromic Performance with High Coloration Efficiency and Switching Stability

Arockiam, Jesin Beneto; Son, Hoseung; Han, Seong Hun; Balamurugan, Gopal; Kim, Yong‐Hoon; Park, Jong Soo

doi:10.1021/acsaem.9b01022

Cited by 37 publications

(16 citation statements)

References 42 publications

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“…The values of CE at λ = 600 nm are on par with that of the most efficient metalorganic ECMs. 23,29,48 The values of CEs at λ = 515 nm and λ = 700 nm in Os−Fe ECM that correspond to the change of oxidation state of Os species are significantly smaller than that of Os in monometallic ECM. It is typical for ECDs with high integrated contrast ratios (i.e., ECD that absorb not in one wavelength but have a broad absorption region) to demonstrate lower coloration efficiencies.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Multichromic Monolayer Terpyridine-Based Electrochromic Materials

Laschuk

Ahmad

Ebralidze

et al. 2020

ACS Appl. Mater. Interfaces

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The article describes novel electrochromic materials (ECMs) that are based on a monolayer consisting of two or three isostructural metal complexes of 4′-(pyridin-4-yl)-2,2’:6′,2’’-terpyridine simultaneously deposited on surface-enhanced support. The support was made by screen printing of indium tin oxide (ITO) nanoparticles on ITO-glass and has a surface area sufficient for a monolayer to give color visible to the naked eye. The ability to separately electrochemically address the oxidation state of the metal centers on the surface (i.e., Co2+/Co3+, Os2+/Os3+, and Fe2+/Fe3+) provides an opportunity to achieve several distinct color-to-color transitions, thus opening the door for constructing monolayer-based multicolor ECMs.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Multichromic Monolayer Terpyridine-Based Electrochromic Materials

Laschuk

Ahmad

Ebralidze

et al. 2020

ACS Appl. Mater. Interfaces

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“… 12 − 14 In addition to well-established inorganic electrochromic materials such as WO 3 , research focuses increasingly on organic molecular compounds and polymers. 15 − 17 Organic materials offer higher coloration efficiencies and better tunability owing to their broad range of possible chemical modifications, while the higher diffusion rates of charge-compensating counterions allow for faster switching times. 18 , 19 …”

Section: Introductionmentioning

confidence: 99%

“…Electrochromism describes reversible color changes of a material in response to an external electronic stimulus. Electrochromic materials have been applied in smart windows, optical displays, and molecular imaging. − In addition to well-established inorganic electrochromic materials such as WO 3 , research focuses increasingly on organic molecular compounds and polymers. − Organic materials offer higher coloration efficiencies and better tunability owing to their broad range of possible chemical modifications, while the higher diffusion rates of charge-compensating counterions allow for faster switching times. , …”

Section: Introductionmentioning

confidence: 99%

Fast-Switching Vis–IR Electrochromic Covalent Organic Frameworks

et al. 2021

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Electrochromic coatings are promising for applications in smart windows or energy-efficient optical displays. However, classical inorganic electrochromic materials such as WO 3 suffer from low coloration efficiency and slow switching speed. We have developed highly efficient and fast-switching electrochromic thin films based on fully organic, porous covalent organic frameworks (COFs). The low band gap COFs have strong vis–NIR absorption bands in the neutral state, which shift significantly upon electrochemical oxidation. Fully reversible absorption changes by close to 3 OD can be triggered at low operating voltages and low charge per unit area. Our champion material reaches an electrochromic coloration efficiency of 858 cm 2 C –1 at 880 nm and retains >95% of its electrochromic response over 100 oxidation/reduction cycles. Furthermore, the electrochromic switching is extremely fast with response times below 0.4 s for the oxidation and around 0.2 s for the reduction, outperforming previous COFs by at least an order of magnitude and rendering these materials some of the fastest-switching frameworks to date. This combination of high coloration efficiency and very fast switching reveals intriguing opportunities for applications of porous organic electrochromic materials.

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“…In MSPs, the polymer backbone (one-dimensionally (1D) linear, two-dimensionally (2D) nanosheeted, or three-dimensionally (3D) hyperbranched structure) is controllable by changing the combination of the multitopic ligands and the metal species. − A linear structure of Fe(II)-based MSP composed of bis(terpyridyl)benzene (Figure b) shows a blue color because of the MLCT absorption around 580 nm. − A 2D nanosheet structure of Fe(II)-based MSP with tris-phenanthroline (Figure c) exhibits a red color because of the MLCT absorption abound 500 nm . Inspired by these results, we designed an asymmetrical ditopic ligand, 5-(4-([2,2′:6′,2″-terpyridin]-4′-yl)phenyl)-1,10-phenanthroline ( L ), for the preparation of a hyperbranched Fe(II)-based MSP with two MLCT absorptions of the Fe(II)-terpyridine moieties and Fe(II)-phenanthroline moieties.…”

Section: Resultsmentioning

confidence: 99%

One-Step Synthesis of a Three-Dimensionally Hyperbranched Fe(II)-Based Metallo-Supramolecular Polymer Using an Asymmetrical Ditopic Ligand for Durable Electrochromic Films with Wide Absorption, Large Optical Contrast, and High Coloration Efficiency

Narayana

Mondal

Rana

et al. 2021

ACS Appl. Electron. Mater.

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For the development of durable electrochromic (EC) materials with wide absorption, large optical contrast, and high coloration efficiency, a threedimensionally hyperbranched Fe(II)-based metallo-supramolecular polymer (polyFe-3D) was one-step synthesized by the complexation of an Fe(II) salt and an asymmetrical ditopic ligand (L) containing terpyridine (tpy) and phenanthroline (phen) moieties, according to the formation of a 1:2 complex of Fe(II) and tpys (Fetpys) and a 1:3 complex of Fe(II) and phens (Fe-phens). The formation of Fe-tpys and Fe-phens was confirmed by the appearance of two metal-to-ligand charge transfer (MLCT) absorptions in the visible area during the titration experiment. The molecular weight (M w ) of polyFe-3D was determined to 3.96 × 10 5 Da by a size-exclusion chromatography−viscometry measurement. PolyFe-3D with the two different Fe(II) complexes (Fe-typs and Fe-phens) exhibited a pair of redox waves for Fe(II/III) (E 1/2 = 0.74 V vs Ag/Ag + ) reversibly in the cyclic voltammograms. The linear relationship between the peak current and the root of the scan rate during redox suggested a diffusion-controlled redox reaction. The spin-coated polymer film showed reversible EC changes between magenta and pale green, caused by the redox of Fe(II/III). A wide visible region from 430 to 640 nm was covered with the two MLCT absorptions of the Fe-tpys and Fe-phens moieties. The broad MLCT absorption disappeared upon applying 1.2 V vs Ag/Ag + and reappeared at 0 V vs Ag/Ag + . The EC changes were revealed to have both a large transmittance change (ΔT) with 70% at 573 nm and a very high coloration efficiency (η) with 689 cm 2 /C. The coloration efficiency exceeded those of the reported linear (one-dimensional), two-dimensional nanosheeted, and three-dimensional hyperbranched Fe(II)-based metallo-supramolecular polymers. A polyFe-3D film showed high durability for the EC changes of more than 1000 cycles. A solid-state simple device fabricated using polyFe-3D exhibited reversible EC changes of more than 1000 cycles without degradation.

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Iron Phthalocyanine Incorporated Metallo-Supramolecular Polymer for Superior Electrochromic Performance with High Coloration Efficiency and Switching Stability

Cited by 37 publications

References 42 publications

Multichromic Monolayer Terpyridine-Based Electrochromic Materials

Multichromic Monolayer Terpyridine-Based Electrochromic Materials

Fast-Switching Vis–IR Electrochromic Covalent Organic Frameworks

One-Step Synthesis of a Three-Dimensionally Hyperbranched Fe(II)-Based Metallo-Supramolecular Polymer Using an Asymmetrical Ditopic Ligand for Durable Electrochromic Films with Wide Absorption, Large Optical Contrast, and High Coloration Efficiency

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