Porphyrin Self-Assembly at Electrochemical Interfaces:  Role of Potential Modulated Surface Mobility

He, Yufan; Ye, Tao; Borguet, Eric

doi:10.1021/ja026115f

Cited by 117 publications

(141 citation statements)

References 22 publications

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“…This corresponds to about 2.2 monolayers, assuming that each molecule occupies an area of 1.55 × 1.55 nm 2 , as determined by STM. 13 The magnitude of the oxidation peak clearly shows that multilayers of TPyP can be adsorbed on Au(111) and survive the rinsing and transfer to another electrochemical cell.…”

Section: Cyclic Voltammetry Resultsmentioning

confidence: 99%

“…This explanation seems in contradiction with our previous STM result that the interaction between TPyP molecules and the Au(111) surface is strong at a high electrode potential but weak at a low electrode potential. 13 However, the strong molecule-substrate interaction, deduced from STM, involves only the first layer and not the multilayer.…”

Section: Cyclic Voltammetry Resultsmentioning

confidence: 99%

“…4 In a previous report, we demonstrated that in an electrochemical environment the interaction between adsorbed 5,10,-15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP, Scheme 1) and the substrate Au(111) is tunable. 13 The adsorbate-substrate interaction was modified by adjusting the surface charge via external control of the electrode potential. It was shown that the formation of an ordered TPyP adlayer can be controlled by surface charge.…”

Section: Introductionmentioning

confidence: 99%

“…It was shown that the formation of an ordered TPyP adlayer can be controlled by surface charge. 13 Adsorption on positively charged surfaces results in disordered adlayers, due to excessive moleculesubstrate interactions. 13 Ordered porphyrin monolayers can be prepared by adsorption at potentials between 0.2 and -0.2 V SCE , where the surface is expected to be negatively charged (the potential of zero charge of reconstructed Au(111) in 0.1 M H 2 -SO 4 is about 0.…”

Section: Introductionmentioning

confidence: 99%

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Adsorption and Electrochemical Activity: An In Situ Electrochemical Scanning Tunneling Microscopy Study of Electrode Reactions and Potential-Induced Adsorption of Porphyrins

Borguet

2006

J. Phys. Chem. B

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The effect of adsorption on molecular properties and reactivity is a central topic in interfacial physical chemistry. At electrochemical interfaces, adsorbed molecules may lose their electrochemical activity. The absence of in situ probes has hindered our understanding of this phenomenon and electrode reactions in general. In this work, classical electrochemistry and electrochemical scanning tunneling microscopy (EC-STM) were combined to provide molecular level insight into electrochemical reactions and the molecular adsorption state at the electrolyte-electrode interface. The metal-free porphyrin 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP) adsorbed on Au(111) in 0.1 M H 2 SO 4 solution was chosen as a model system. TPyP is found to irreversibly adsorb on Au(111) over a wide range of potentials, from -0.25 to 0.6 V SCE . The adsorption state of TPyP has a dramatic effect on its electrochemistry. Preadsorbed, oxidized TPyP displays no well-defined cathodic peaks in cyclic voltammograms in sharp contrast to solution-phase TPyP. Our present work provides direct, molecular level evidence of the electrochemically "invisible" species. Electrochemical activity of absorbed species is recovered by allowing the oxidized molecule sufficient time (tens of minutes) to reduce. The redox state of adsorbed TPyP also affects the nature of the adsorption. Oxidized species can apparently only form monolayers. However, multilayers, stable enough to be imaged by STM, can form when the adsorbed TPyP is in the reduced state. This suggests that by controlling the electrochemistry one can either promote or suppress the formation of multilayers.

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Section: Cyclic Voltammetry Resultsmentioning

confidence: 99%

Section: Cyclic Voltammetry Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Adsorption and Electrochemical Activity: An In Situ Electrochemical Scanning Tunneling Microscopy Study of Electrode Reactions and Potential-Induced Adsorption of Porphyrins

Borguet

2006

J. Phys. Chem. B

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“…These processes will play a critical role in the so-called ''bottom-up'' strategy of nanofabrication. Therefore, understanding the organization of molecules on solid surfaces is important, both from a fundamental and applied perspective, for the construction of surface molecular nanostructures and nanodevices (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13). A self-organized molecular pattern with control of structure and derived concomitant function could provide promising materials for the construction of nanodevices that cannot be prepared by conventional microfabrication.…”

mentioning

confidence: 99%

Mesoscopic self-organization of a self-assembled supramolecular rectangle on highly oriented pyrolytic graphite and Au(111) surfaces

Gong

Wan

Yuan

et al. 2005

Proc. Natl. Acad. Sci. U.S.A.

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A self-assembled supramolecular metallacyclic rectangle was investigated with scanning tunneling microscopy on highly oriented pyrolytic graphite and Au(111) surfaces. The rectangles spontaneously adsorb on both surfaces and self-organize into well ordered adlayers. On highly oriented pyrolytic graphite, the long edge of the rectangle stands on the surface, forming a 2D molecular network. In contrast, the face of the rectangle lays flat on the Au(111) surface, forming linear chains. The structures and intramolecular features obtained through high-resolution scanning tunneling microscopy imaging are discussed.metallacyclic macrocycle ͉ scanning tunneling microscopy ͉ molecular adlayer ͉ molecular orientation S elf-organization (1) and self-assembly (2) are critical and necessary processes in all living organisms and are of ever increasing importance in chemistry and material science. These processes will play a critical role in the so-called ''bottom-up'' strategy of nanofabrication. Therefore, understanding the organization of molecules on solid surfaces is important, both from a fundamental and applied perspective, for the construction of surface molecular nanostructures and nanodevices (3-13). A self-organized molecular pattern with control of structure and derived concomitant function could provide promising materials for the construction of nanodevices that cannot be prepared by conventional microfabrication. The arrangement of adsorbed molecules onto a surface depends on both intermolecular and molecule-surface interactions. For example, Hipps and colleagues (3, 4) prepared a self-organized 2D bifunctional structure on a Au (111) Metal-containing macrocycles with high symmetry and precise architecture are a new class of promising supramolecules for future application in nanotechnology because of their exact shape and size, as well as magnetic, photophysical, and electrostatic properties (14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27). In this article, we describe scanning tunneling microscopy (STM) studies of the self-assembled supramolecular metallacyclic rectangle, cyclobis [(1, ) 2 )anthracene)(1,4Ј-bis(4-ethynylpyridyl)benzene](PF 6 ) 4 , (Fig. 1) (28). The dimensions of a single rectangle molecule were independently determined to be 3.1 nm long by 1.2 nm wide, from the previously reported x-ray crystallographic data (28). The molecular adlayers were prepared on highly oriented pyrolytic graphite (HOPG) and Au(111) surfaces to investigate the effect of substrate on adlayer formation. The molecules self-organize into well ordered 2D adlayers on both surfaces, and high-resolution STM results clearly reveal an intact rectangle on both HOPG and Au (111) surfaces, but the symmetry and molecular orientation the molecules adopt depends on the substrate. Materials and MethodsChemicals. The PF 6 Ϫ salt of the rectangle was prepared analogously to the ClO 4 Ϫ salt previously reported (28), substituting KPF 6 for NaClO 4 .Substrates. HOPG (quality ZYB) was purchased from Digital Instruments (Santa Barbar...

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Metal–Electrolyte Interfaces

Nowicki¹,

Wandelt²

2020

Surface and Interface Science

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Porphyrin Self-Assembly at Electrochemical Interfaces: Role of Potential Modulated Surface Mobility

Cited by 117 publications

References 22 publications

Adsorption and Electrochemical Activity: An In Situ Electrochemical Scanning Tunneling Microscopy Study of Electrode Reactions and Potential-Induced Adsorption of Porphyrins

Adsorption and Electrochemical Activity: An In Situ Electrochemical Scanning Tunneling Microscopy Study of Electrode Reactions and Potential-Induced Adsorption of Porphyrins

Mesoscopic self-organization of a self-assembled supramolecular rectangle on highly oriented pyrolytic graphite and Au(111) surfaces

Metal–Electrolyte Interfaces

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