Photoelectric conversion at a [Ru(bpy)<sub>3</sub>]<sup>2+</sup>-based metallic triad anchored on ITO surface

Farran, Rajaa; Jouvenot, Damien; Chauvin, Jérôme; Deronzier, Alain

doi:10.1039/c4dt01884b

Cited by 9 publications

(20 citation statements)

References 28 publications

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“…For comparison with previously published data, all potentials given in the text and in Table S2 † have been converted to values relative to the saturated calomel electrode (SCE) by using the following relationship: E(SCE) ¼ E(Ag/AgNO 3 ) + 298 mV. 29 Adsorption experiments. The adsorption of methylene blue (MB) and crystal violet (CV) (Scheme 2) in the presence of H 2 TMAPP and [Co II (TMAPP)] was carried out in batch mode with constant agitation.…”

Section: Synthesismentioning

confidence: 99%

A new cobalt(ii)meso-porphyrin: synthesis, characterization, electric properties and application in the catalytic degradation of dyes

et al. 2020

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Section: Synthesismentioning

confidence: 99%

A new cobalt(ii)meso-porphyrin: synthesis, characterization, electric properties and application in the catalytic degradation of dyes

et al. 2020

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“…23 This strategy takes advantage of the strong self-assembling interaction between oxygen-containing functional groups such as phosphonates with ITO and SiO 2 surface as well as the efficient chelation abilities of terpyridine ligands with first row transition metals (scheme 3).…”

Section: Elaboration and Characterization Of Modified Ito/[co Ii_ Ru mentioning

confidence: 99%

“…On the other hand, the ITO/triad system behaved as a photoanode in the presence of TEOA at an applied potential of 0.12 V. The good chemical and photochemical stability of the triad anchored with phosphonate groups on ITO was already controlled over 1.5 hours of alternating irradiation cycles of 20 s. 23 As an extension of this work this linear triad could be built between two nano-electrodes in order to form photoactivable molecular junctions taking advantage of the rigid and linear backbone. Ongoing work in our laboratory includes also the formation of 1D coordination polymers with other kind of metallic centers coupling photosensitive and catalytic activities.…”

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confidence: 99%

Photoinduced Charge Separation within Metallo-supramolecular Wires Built around a [Ru(bpy)₃]²⁺–Bisterpyridine Linear Entity

Farran

Jouvenot

Génnaro

et al. 2016

ACS Appl. Mater. Interfaces

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A [Ru(bpy)3](2+)-like complex (L1) bearing two free terpyridine groups at the 5 and 5' positions of the same bipyridine, linked by the rigid and linear 2,5-dimethyl phenylene bridges has been synthesized to open access to two classes of linear molecular wires with photosensitive properties: a bimetallic coordination polymer and an inorganic triad. In this Research Article, we report on the synthesis and characterization of the resulting [{Ru(II_)Fe(II)}n](4n+) alternated bimetallic polymer and the [Co(III_)Ru(II_)Fe(II)](7+) triad based on the building block L1. The [{Ru(II_)Fe(II)}n](4n+) polymer is fully characterized in solution. Cyclic voltammetry and emission lifetime measurements show that the bridging ligand allows interaction between the metal centers in the excited state despite the lack of interactions in the ground state. Under visible irradiation, the polymer can be fully oxidized in the presence of a sacrificial electron acceptor in solution. Thin robust films of the polymer are easily obtained on ITO by a simple electrochemical procedure based on an electroreduction adsorption process. The ITO/[{Ru(II_)Fe(II)}n](4n+)-modified electrode behaves as a photocathode under irradiation in the presence of ArN2(+). The magnitude of the photocurrent is dependent on the film thickness, probably limited by the diffusion of charge in thicker film. On the other hand L1 is also used to construct a well-ordered triad in association with Co(III) and Fe(II) metallic centers as electron acceptor and donor, respectively. The metallic triad is anchored on ITO or on a SiO2 wafer, starting from a terpyridine phosphonate modified surface. AFM images prove the presence of the triad in a linear upward orientation. Irradiation of the ITO/[Co(III_)Ru(II_)Fe(II)](7+) modified surface in the presence of triethanolamine in CH3CN induces the generation of an anodic photocurrent of around 30 μA.cm(-2). The photocurrent density generated by the ITO/[Co(III_)Ru(II_)Fe(II)](7+) electrode, appears to be more stable than in the case of ITO/[{Ru(II_)Fe(II)}n](4n+) because of the presence of the anchoring group. Moreover, this photocurrent magnitude represents an enhancement of 30% compared to our previous triad ( Dalton Trans. 2014 , 43 , 12156 - 12159 ), proving the advantage of a linear and rigid spacer for the construction of such molecular assemblies with photoinduced charge transfer abilities.

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“…30 Moreover, the magnitude of the photocurrent is significantly increased when the three subunits (electron acceptor−photosensitizer−electron donor) are linked in a well-organized assembly. 31 However, the use of an ITO electrode to build photoactive systems does not allow a full characterization of the molecular architecture and of the electron-transfer processes due to the surface roughness and the relatively low electrical conductivity of ITO. In contrast, gold is more conductive and can easily be deposited as a thin layer on various substrates or be shaped to a microball, which minimizes both ohmic losses and time constant of the electrochemical cell.…”

Section: ■ Introductionmentioning

confidence: 99%

“…34 The [Ru(bpy) 2 (bpyOtpy)] 2+ metalloligand was prepared in three steps following a published procedure. 31 4′-(p-thiophenyl)-2,2′:6′,2″terpyridine (ttpy-SH) was synthesized according to the literature. 35 Gold Electrode and Grafting Process.…”

Section: ■ Introductionmentioning

confidence: 99%

Photoactive Molecular Dyads [Ru(bpy)₃–M(ttpy)₂]ⁿ⁺ on Gold (M = Co(III), Zn(II)): Characterization, Intrawire Electron Transfer, and Photoelectric Conversion

et al. 2018

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We propose in this work a stepwise approach to construct photoelectrodes. This takes advantage of the self-assembly interactions between thiol with a gold surface and terpyridine ligands with first-row transition metals. Here, a [Ru(bpy)] photosensitive center bearing a free terpyridine group has been used to construct two linear dyads on gold (Au/[Zn-Ru] and Au/[Co-Ru]). The stepwise construction was characterized by electrochemistry, quartz crystal microbalance, and atomic force microscopy imaging. The results show that the dyads behave as rigid layers and are inhomogeneously distributed on the surface. The surface coverages are estimated to be in the order of 10 mol cm. The kinetics of the heterogeneous electron transfer is determined on modified gold ball microelectrodes using Laviron's formula. The oxidation rates of the terminal Ru(II) subunits are estimated to be 700 and 2300 s for Au/[Zn-Ru] and Au/[Co-Ru], respectively. In the latter case, the rate is limited by the kinetics of electron transfer between an intermediate Co(II) center and the gold surface. For Au/[Zn-Ru], the Zn-bis-terpyridine center is not involved in the electron-transfer process and the oxidation of the Ru(II) subunit occurs through a superexchange process. In the presence of a tertiary amine in solution, the electrodes at a bias of 0.12 V behave as photoanodes when subjected to visible light irradiation. The magnitude of the photocurrent is around 10 μA cm for Au/[Co-Ru] and 5 μA cm for Au/[Zn-Ru], proving the importance of an electron relay on the photon-to-current conversion. The results suggest an efficient conversion for Au/[Co-Ru], since each bound dyad, once excited, injects an electron around 10 times per second.

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Photoelectric conversion at a [Ru(bpy)₃]²⁺-based metallic triad anchored on ITO surface

Cited by 9 publications

References 28 publications

A new cobalt(ii)meso-porphyrin: synthesis, characterization, electric properties and application in the catalytic degradation of dyes

A new cobalt(ii)meso-porphyrin: synthesis, characterization, electric properties and application in the catalytic degradation of dyes

Photoinduced Charge Separation within Metallo-supramolecular Wires Built around a [Ru(bpy)₃]²⁺–Bisterpyridine Linear Entity

Photoactive Molecular Dyads [Ru(bpy)₃–M(ttpy)₂]ⁿ⁺ on Gold (M = Co(III), Zn(II)): Characterization, Intrawire Electron Transfer, and Photoelectric Conversion

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Photoelectric conversion at a [Ru(bpy)3]2+-based metallic triad anchored on ITO surface

Cited by 9 publications

References 28 publications

A new cobalt(ii)meso-porphyrin: synthesis, characterization, electric properties and application in the catalytic degradation of dyes

A new cobalt(ii)meso-porphyrin: synthesis, characterization, electric properties and application in the catalytic degradation of dyes

Photoinduced Charge Separation within Metallo-supramolecular Wires Built around a [Ru(bpy)3]2+–Bisterpyridine Linear Entity

Photoactive Molecular Dyads [Ru(bpy)3–M(ttpy)2]n+ on Gold (M = Co(III), Zn(II)): Characterization, Intrawire Electron Transfer, and Photoelectric Conversion

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Photoelectric conversion at a [Ru(bpy)₃]²⁺-based metallic triad anchored on ITO surface

Photoinduced Charge Separation within Metallo-supramolecular Wires Built around a [Ru(bpy)₃]²⁺–Bisterpyridine Linear Entity

Photoactive Molecular Dyads [Ru(bpy)₃–M(ttpy)₂]ⁿ⁺ on Gold (M = Co(III), Zn(II)): Characterization, Intrawire Electron Transfer, and Photoelectric Conversion