Photocatalytic Reactions at Microcrystalline fac-Mn(CO)3(η2-Ph2PCH2PPh2)Cl−Electrode−Aqueous (Electrolyte) Interfaces

Eklund, John C.; Bond, Alan M.

doi:10.1021/ja9908974

Cited by 15 publications

(4 citation statements)

References 29 publications

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“…Note that due to a distinct oddeven effect for the dipole moment of alkanethiols [32] and the properties of the corresponding organic electronic devices, [13] it would be more accurate to define the variation of the potential with respect to a pair of -CH 2 -groups, but we will follow the definition given in the experimental papers [45,46] to facilitate the comparison. The difference between the results of atomistic calculations and those obtained using Equation 5 can be attributed to two factors. Firstly, the dipole moment of the molecule in the SAM differs from the dipole of an optimized gas phase molecule due to chemical bond formation with the gold surface and geometrical changes.…”

Section: Ch 3 -Terminated Monolayersmentioning

confidence: 86%

“…[1][2][3][4][5][6][7][8] In nanotechnology the adsorption of organic layers onto metal surfaces is widely used as a method for the work function manipulation of metal electrodes in order to achieve electron transport in organo-electronic devices. [9][10][11][12][13][14] Several effects may influence the interfacial dipole moment of an organic film on a metal surface, responsible for the shift of metal work function: a dipole moment of organic molecules in the film, which is determined by the dipole moment of an isolated molecule and the molecule's charge rearrangement due to intermolecular interactions in the film, the charge transfer between the molecules and the metal leading to the formation of an additional dipole at the interface.…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular Dipole Coupling and Depolarization in Self‐Assembled Monolayers

Sushko

Shluger

2008

Adv Funct Materials

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Quantum mechanical and classical atomistic computational methods are used to simulate the chain‐length dependence of depolarization effects in S(CH2)n−1CH3 and S(CH2)n−1COOH self‐assembled monolayers on gold (111) surface. These calculations show that due to weak cooperative effects, the electrostatic properties of alkanethiol monolayers are well described by the gas phase dipole moments of the molecules. However, depolarization in monolayers with the molecules carrying head‐ and tail‐group dipoles, such as COOH‐terminated monolayers, strongly depends on the degree of intramolecular dipole coupling. Thus the electrostatic properties of self‐assembled monolayers can be engineered by changing the length of the aliphatic spacer between the polar groups. The transition from strong to weak coupling regime was found to be accompanied by the change in the sign of the asymptotic value of electrostatic potential above the surface of the monolayers and hence in the sign of the metal work function change. Therefore, the use of weakly polarizable spacers between the polar groups inside the molecules forming the SAM is beneficial for accessing a wider range of work‐function changes.

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Section: Ch 3 -Terminated Monolayersmentioning

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Intramolecular Dipole Coupling and Depolarization in Self‐Assembled Monolayers

Sushko

Shluger

2008

Adv Funct Materials

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“…Alternatively (or complementarily), analytical information can be derived from studies of the catalytic [169][170][171][172] and photoelectrocatalytic [173] effects of selected electrochemical processes. This involves the use of a redox probe in the electrolyte able to be catalyzed by the analyte, as previously mentioned.…”

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confidence: 99%

Electroanalytical chemistry for the analysis of solids: Characterization and classification (IUPAC Technical Report)

Doménech‐Carbó

Labuda

Scholz

2012

Pure and Applied Chemistry

155

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Solid state electroanalytical chemistry (SSEAC) deals with studies of the processes, materials, and methods specifically aimed to obtain analytical information (quantitative elemental composition, phase composition, structure information, and reactivity) on solid materials by means of electrochemical methods. The electrochemical characterization of solids is not only crucial for electrochemical applications of materials (e.g., in batteries, fuel cells, corrosion protection, electrochemical machining, etc.) but it lends itself also for providing analytical information on the structure and chemical and mineralogical composition of solid materials of all kinds such as metals and alloys, various films, conducting polymers, and materials used in nanotechnology. The present report concerns the relationships between molecular electrochemistry (i.e., solution electrochemistry) and solid state electrochemistry as applied to analysis. Special attention is focused on a critical evaluation of the different types of analytical information that are accessible by SSEAC.

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confidence: 99%

Rough and Fine Tuning of Metal Work Function via Chemisorbed Self‐Assembled Monolayers

Sushko

Shluger

2009

Advanced Materials

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Many chemical and biochemical processes in nature involve charge transport across organic/inorganic interfaces, [1][2][3][4][5][6][7][8] which determines the performance of organic electronic devices. [9][10][11][12][13][14] To achieve efficient charge transport between the electrode and organic molecules, the metal work function has to match the energy level of either the highest occupied or lowest unoccupied molecular orbitals of the molecule, which usually requires adjustments in the metal work function. One of the most common methods used for modification of metal work functions is the adsorption of organic layers. By adsorbing an organic layer onto the electrode surface, one creates a dipole barrier for the charge-carrier transport between the electrode and the organic electronic device. The surface dipole of the organic film depends on the dipole moment of the molecules forming the film, their electrostatic interactions and, for chemisorbed layers, the dipole at the interface due to partial charge transfer between the molecules and the surface. In particular, self-assembled monolayers (SAMs) of thiols are widely used for modification of the work function of gold electrodes. It has been shown that for these systems the charge transfer between the molecules and the gold is under 0.05e and, therefore, the chemical component of the interfacial dipole is negligibly small.[15] The work-function change in these systems is thus mainly determined by the dipole moments of individual molecules, the structure of the monolayer, and dipole depolarization in the SAM. The electrostatic interaction inside SAMs leads to a decrease in the surface dipole of the SAM, compared to that expected from the gas-phase dipoles. [16][17][18] Depolarization effects thus significantly decrease the accessible range of changes in SAM-induced metal work functions.The inevitable presence of defects in the SAMs, such as rotation of the molecules' backbones and changes in the configuration of the tail-group, which is a most common type of gauche defect (Fig. 1a), can also influence the electrostatic interactions in the monolayer. Defects in the monolayers lead to variations in orientation of molecular dipoles in the SAM (Fig. 1a), and, therefore, to local and global variations in the metalwork-function change. Although the nonideal character of SAMs is well-recognized, and confirmed both experimentally and theoretically, [19][20][21] the theoretical studies of depolarization effects in SAMs were until recently still confined to ideal monolayers.Our recent study of HS(CH 2 ) 11 COOH SAMs on gold surfaces showed a strong dependence of SAM depolarization and of the associated metal-work-function change on the structure of the SAM.[22] Here, we report a systematic study of this effect for HS(CH 2 ) n X monolayers, where X ¼ CH 3 , CF 3 , COOH, on Au (111) surfaces, and suggest a general method for rough and fine tuning of metal work functions using SAMs. We identify the polarizability of the polar groups of organic molecules as the main factor dete...

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Photocatalytic Reactions at Microcrystalline fac-Mn(CO)₃(η²-Ph₂PCH₂PPh₂)Cl−Electrode−Aqueous (Electrolyte) Interfaces

Cited by 15 publications

References 29 publications

Intramolecular Dipole Coupling and Depolarization in Self‐Assembled Monolayers

Intramolecular Dipole Coupling and Depolarization in Self‐Assembled Monolayers

Electroanalytical chemistry for the analysis of solids: Characterization and classification (IUPAC Technical Report)

Rough and Fine Tuning of Metal Work Function via Chemisorbed Self‐Assembled Monolayers

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