Molecular assemblies and redox reactions of zinc(II) tetraphenylporphyrin and zinc(II) phthalocyanine on Au(1 1 1) single crystal surface at electrochemical interface

Yoshimoto, Soichiro; Tsutsumi, Eishi; Suto, Koji; Honda, Yosuke; Itaya, Kingo

doi:10.1016/j.chemphys.2005.04.038

Cited by 75 publications

(100 citation statements)

References 42 publications

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“…It is reported that the contrast of STM images of redox molecules is highly dependent on the tunneling probability associated with the electronic configuration of the molecules, which is successfully explained in terms of orbital-mediated tunneling. 21,22 In the case of triruthenium clusters, molecular orbitals (MOs) are constructed by d³ orbitals on each Ru atom and a p³ orbital of the central is shown, where M 0 , M t , and M¨are the number of spots assigned to 1 + at t = 0, t, and¨, respectively.…”

Section: Resultsmentioning

confidence: 99%

In Situ Scanning Tunneling Microscopy Observation of Metal–Cluster Redox Interconversion and CO Dissociation Reactions at a Solution/Au(111) Interface

Noda¹,

Uehara²,

Abe³

et al. 2009

Bulletin of the Chemical Society of Japan

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We present here an in situ scanning tunneling microscopy (STM) study of potential-induced reactions of oxo-centered acetato-bridged triruthenium clusters on Au(111) under electrochemical conditions, in which (i) reversible interconversion between two different redox states of the cluster and (ii) spontaneous dissociation of CO from the cluster were probed and visualized. It is known that the triruthenium complex [Ru 3 (® 3 -O)(®-CH 3 COO) 6 ) were independently examined with in situ STM in a monolayer level by visualizing molecular-sized spots showing a different extent of brightness in STM images. We show here that the molecular-sized spots corresponding to 1, 1 + , and 2 + are resolved by their brightness, which strongly depends on both the oxidation states and the ligand nature of the clusters. By employing multiple fast scans at an applied potential of +0.80 V vs. Ag/AgCl, we obtained STM images that follow the irreversible 1 + ¼ 2 + reaction on the surface, from which a rate constant of the CO release was calculated to be 1.9 («0.2) © 10 ¹2 s ¹1 (25°C; in contact with 0.1 mol dm ¹3 aqueous HClO 4 solution). The difference in brightness of the molecular spots is rationalized in terms of orbital-mediated tunneling by considering the difference in electronic states of the d³p³ system in the ® 3 -O triruthenium cluster.Direct probe and analysis of atomic and molecular processes that occur at solidsolution interfaces have become increasingly essential for nanometer-scale science and technology. One crucial experimental challenge is to develop practical methods that allow direct observation of chemical reactions at a molecular or monolayer level. Scanning tunneling microscopy (STM) is a powerful technique for structural characterization of atoms, molecules, and supramolecular assemblies on surfaces and the enormous utility has been particularly manifested in probing atomic-scale processes in ultrahigh-vacuum. 15 While the in situ technique of STM has recently seen rapid progress for structural identification of molecules on well-defined electrode surfaces, 614 direct probe of chemical reactions which are triggered by applied potentials still remains a significant challenge.In this paper, we describe a successful probe and analysis of potential-induced chemical reactions of self-assembled monolayers (SAMs) of an oxo-centered acetato-bridged trinuclear ruthenium cluster 15,16 [{Ru 3 (® 3 -O)(®-CH 3 COO) 6 -(mpy)(CO)} 2 (®-C 10 py)] (mpy = 4-methylpyridine, C 10 py = {(NC 5 H 4 )CH 2 NHC(O)(CH 2 ) 10 S} 2 ) (Figure 1a) 17 at a solution/Au(111) interface with the in situ STM technique. Interfacial reactions examined here are illustrated in Figure 1b + is the one-electron-oxidized form of 1, while 2 + represents a cat-

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Section: Resultsmentioning

confidence: 99%

In Situ Scanning Tunneling Microscopy Observation of Metal–Cluster Redox Interconversion and CO Dissociation Reactions at a Solution/Au(111) Interface

Noda¹,

Uehara²,

Abe³

et al. 2009

Bulletin of the Chemical Society of Japan

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“…Using the same techniques, half-wave redox potentials of a substituted phthalocyanine with hexyloxy groups in non-peripheral positions and chlorinated phenyl groups in peripheral positions [40] have also been calculated in benzonitrile solution, and the results are also gathered in Table 2. Yoshimoto et al [17] Figure 10 are also identified on all the curves in Figure 11 and are summarized in Table 3. A comparison of these values with the half-wave/formal potentials reported in Table 2 permits Therefore, freshly deposited LB films incorporating oxyZnPc undertake redox processes on the surface of a GCE electrode in an aqueous electrolyte.…”

Section: Langmuir-blodgett Filmsmentioning

confidence: 99%

“…Thus, only a few works have focused in thin films of ZnPc [7,8,[14][15][16][17][18]; Schunemann et al [7], Peisert et al [8] 5 and Schöllhorn et al [14,15] investigated films obtained by vapour deposition, Ozoemena et al…”

Section: Introductionmentioning

confidence: 99%

“…[16] studied self-assembled monolayers, Yoshimoto et al [17] used adlayers in their studies and Chowdhury et al [18] obtained thin films of ZnPc by vapour deposition and a subsequent annealing process. The LB technique for the assembly of ZnPc has been used in a limited number of works [1,9,[19][20][21][22][23], and recently Qiu et al [24] used the horizontal transfer technique (Langmuir-Schaefer, LS).…”

Section: Introductionmentioning

confidence: 99%

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Characterization of Langmuir and Langmuir–Blodgett films of an octasubstituted zinc phthalocyanine

et al. 2014

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“…85,86 Adsorption of benzene on Au(111) surfaces is weak under these conditions, which encouraged us to investigate adlayers of water-insoluble organic molecules without interference from the adsorption of the solvent (benzene). Figure 4 shows typical high-resolution STM images of each molecular adlayer of MTPP and MPc.…”

Section: Porphyrin and Phthalocyanine Assemblies On Goldmentioning

confidence: 99%

Recent Progresses of Electrochemical Surface Science &sim;Importance of Surface Imaging with Atomic Scale&sim;

Itaya

2015

Electrochemistry

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In the electrochemical surface science during the past 20 years, in-situ electrochemical scanning tunneling microscopy (EC-STM) and atomic force microscopy (AFM) have made significant contribution to understand various electrochemical processes with atomic scale. For examples, the underpotential deposition of copper, silver, and other metal ions; the specific adsorption of anions such as iodine and sulfate/bisulfate ions; electrochemical etching processes of metals and semiconductors and the molecular assembly of many organic molecules, such as metalloporphyrins, and metallophthalocyanines. Furthermore, we have recently developed a high resolution laser confocal microscope, combined with a differential interference contrast microscope, which enables to follows fast dynamic electrochemical processes at atomic height resolution in relatively large areas. It has been shown for the first time that single atomic steps of metals can be successfully seen by the newly developed optical microscope. Surface imaging techniques provide local pictures of electrode processes on the atomic scale, not averaged information in large areas.

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Molecular assemblies and redox reactions of zinc(II) tetraphenylporphyrin and zinc(II) phthalocyanine on Au(1 1 1) single crystal surface at electrochemical interface

Cited by 75 publications

References 42 publications

In Situ Scanning Tunneling Microscopy Observation of Metal–Cluster Redox Interconversion and CO Dissociation Reactions at a Solution/Au(111) Interface

In Situ Scanning Tunneling Microscopy Observation of Metal–Cluster Redox Interconversion and CO Dissociation Reactions at a Solution/Au(111) Interface

Characterization of Langmuir and Langmuir–Blodgett films of an octasubstituted zinc phthalocyanine

Recent Progresses of Electrochemical Surface Science &sim;Importance of Surface Imaging with Atomic Scale&sim;

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