Electrochemical Behavior of Sequentially Assembled Homo and Heterolayer Molecular Films Based on Dinuclear Ruthenium Complexes

Nagashima, Takumi; Suzuki, Takashi; Ozawa, Hiroaki; Nakabayashi, Takakazu; Oyama, Makiko; Ishida, Takao; Haga, Masa‐aki

doi:10.1016/j.electacta.2016.04.059

Cited by 8 publications

(7 citation statements)

References 20 publications

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“…Photoirradiation of the ITO|(11) 4 /(12) 4 hetero-multilayer film in CH 3 CN (0.1 M HClO 4 ) at the open circuit potential of +0.45 V produced a cathodic photocurrent. The action spectrum of this film is nearly identical to the UV-vis absorption [22,62]. spectrum of 11, which indicates the inner 11 layers are the main contributor to the photoexcitation, although little photo-response was observed for homo-Ru-complex multilayer films such as ITO|(11) n or ITO|(12) n .…”

Section: Sequentially Assembled Heterolayer Films Of Ru Complexesmentioning

confidence: 75%

“…In addition, potential-step chronoamperometry (PSCA) measurements furnished a relatively small value for the apparent electron-transfer rate, k app (β = 0.014 Å À1 ) [62].…”

Section: Electron-transfer Rate In Homo-multilayer Ru Complex Films On Ito Electrodesmentioning

confidence: 99%

“…Due to the large differences between the potentials of 11 and 12, heterolayer films made from combinations of 11 and 12 exhibited interesting electronic/photonic behaviors such as electron-transfer blocking, rectification, and vectorial photoelectron transfer. Figure 22 shows the CV responses of the heterolayer films ITO|(11) n /(12) n (n = 1, 2, where n stands for the number of layers) and ITO|(12) n /(11) n (n = 1,3) and the alternating heterolayer films ITO|(11/12) 4 and ITO|(12/11) 4 in CH 3 CN (0.1 M HClO 4 ) [22,62]. The ITO|(11) 1 /(12) 1 bilayer heterofilm exhibited four waves (Figure 22a), which correspond to the redox processes from both the inner 11 and outer 12 layers; the Ru(II)-Ru(III)/Ru(III)-Ru(III) process of 11 and the Ru(III)-Ru(III)/Ru(III)-Ru(IV) process of 12 overlap at +1.11 V. However, the peak separation of the outer layer of 12 increased at higher scan rates, while the peak separation for the waves from the inner layer of 11 remained unaffected.…”

Section: Sequentially Assembled Heterolayer Films Of Ru Complexesmentioning

confidence: 99%

“…Consequently, the large cathodic peak at À0.5 V was assigned to the catalytic reduction wave of the 12 film mediated by the reduction process of the inner 11 film. Furthermore, the sequence of the 11 and 12 layers on the ITO electrode leads to characteristic CV responses depending on the sequence and the number of layers, as shown in Figure 22 [62].…”

Section: Sequentially Assembled Heterolayer Films Of Ru Complexesmentioning

confidence: 99%

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Surface-Confined Ruthenium Complexes Bearing Benzimidazole Derivatives: Toward Functional Devices

Haga¹

2022

Ruthenium - An Element Loved by Researchers

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Substitutionally inert ruthenium complexes bearing benzimidazole derivatives have unique electrochemical and photochemical properties. In particular, proton coupled electron transfer (PCET) in ruthenium–benzimidazole complexes leads to rich redox chemistry, which allows e.g. the tuning of redox potentials or switching by deprotonation. Using the background knowledge from acquired from their solution-state chemistry, Ru complexes immobilized on electrode surfaces have been developed and these offer new research directions toward functional molecular devices. The integration of surface-immobilized redox-active Ru complexes with multilayer assemblies via the layer-by-layer (LbL) metal coordination method on ITO electrodes provides new types of functionality. To control the molecular orientation of the complexes on the ITO surface, free-standing tetrapodal phosphonic acid anchor groups were incorporated into tridentate 2,6-bis(benzimidazole-2-yl)pyridine or benzene ligands. The use of the LbL layer growth method also enables “coordination programming” to fabricate multilayered films, as a variety of Ru complexes with different redox potentials and pKa values are available for incorporation into homo- and heterolayer films. Based on this strategy, many functional devices, such as scalable redox capacitors for energy storage, photo-responsive memory devices, proton rocking-chair-type redox capacitors, and protonic memristor devices have been successfully fabricated. Further applications of anchored Ru complexes in photoredox catalysis and dye-sensitized solar cells may be possible. Therefore, surface-confined Ru complexes exhibit great potential to contribute to the development of advanced functional molecular devices.

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Section: Sequentially Assembled Heterolayer Films Of Ru Complexesmentioning

confidence: 75%

“…In addition, potential-step chronoamperometry (PSCA) measurements furnished a relatively small value for the apparent electron-transfer rate, k app (β = 0.014 Å À1 ) [62].…”

Section: Electron-transfer Rate In Homo-multilayer Ru Complex Films On Ito Electrodesmentioning

confidence: 99%

Section: Sequentially Assembled Heterolayer Films Of Ru Complexesmentioning

confidence: 99%

Section: Sequentially Assembled Heterolayer Films Of Ru Complexesmentioning

confidence: 99%

See 2 more Smart Citations

Surface-Confined Ruthenium Complexes Bearing Benzimidazole Derivatives: Toward Functional Devices

Haga¹

2022

Ruthenium - An Element Loved by Researchers

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“…Various approaches have been implemented to achieve the immobilization of Ru complexes. They have been deposited as thin films using spin coating [15], or using layer by layer assembly [16].…”

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confidence: 99%

Multi-modal surface grafting of [trans-bis(aminodiphenylphosphine) terpyridine-Ru(II)Cl]+Cl− complex onto glassy carbon electrode

Trần

Pellon

Jeannin

et al. 2018

Electrochimica Acta

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modal surface grafting of [trans-bis(aminodiphenylphosphine) terpyridine-Ru(II)Cl]+Cl-complex onto glassy carbon electrode. Electrochimica Acta, Elsevier, 2018, 259, pp.Abstract: The design of a ruthenium-terpyridine complex having 4-aminobenzyldiphenylphosphine as remote ligands in a trans arrangement ([Ru(trans-PN) 2 (trpy)Cl] + Cl -,[trans-bis(aminodiphenylphosphine) terpyridine-Ru(II)Cl] + Cl -) is shown to be a highly versatile approach for the immobilization of the organometallics at a carbon surface. Three distinct strategies could be then successfully employed to achieve the grafting of the complex, namely i) the electroreduction of the corresponding in situ produced diazonium cation, ii) the electrooxidation of the aromatic amine moiety in the presence of a base and iii) an anodic electropolymerisation in the absence of base. The modified surfaces were characterized by electrochemical or Scanning Electron Microscopy (SEM) studies. The reported approach allows a clean modulation of film thickness and anchoring modes, particularly useful for a given design of ruthenium containing films dedicated to a given application. In this context, the polymer films which contain the largest surface concentration of active ruthenium were employed as immobilized catalyst for oxidation of benzyl alcohol in water, allowing a test of the catalytic activity of the complexes as grafted materials.

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Metal-Carbon Bonds of Heavier Group 7 and 8 Metals (Tc, Re, Ru, Os): Mononuclear Tc/Re/Ru/Os Complexes With Metal-Carbon Bonds

Wei

Jia

2021

Comprehensive Coordination Chemistry III

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Electrochemical Behavior of Sequentially Assembled Homo and Heterolayer Molecular Films Based on Dinuclear Ruthenium Complexes

Cited by 8 publications

References 20 publications

Surface-Confined Ruthenium Complexes Bearing Benzimidazole Derivatives: Toward Functional Devices

Surface-Confined Ruthenium Complexes Bearing Benzimidazole Derivatives: Toward Functional Devices

Multi-modal surface grafting of [trans-bis(aminodiphenylphosphine) terpyridine-Ru(II)Cl]+Cl− complex onto glassy carbon electrode

Metal-Carbon Bonds of Heavier Group 7 and 8 Metals (Tc, Re, Ru, Os): Mononuclear Tc/Re/Ru/Os Complexes With Metal-Carbon Bonds

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