STM Observation of Alkyl-Chain-Assisted Self-Assembled Monolayers of Pyridine-Coordinated Porphyrin Rhodium Chlorides

Ikeda, Taichi; Asakawa, Masumi; Goto, Midori; Miyake, Koji; Ishida, Takao; Shimizu, Toshimi

doi:10.1021/la049577a

Cited by 71 publications

(61 citation statements)

References 80 publications

(33 reference statements)

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“…23 In contrast, STM observations of mixtures containing free base porphyrins and Rh(Cl)porphyrins with axially bound pyridines show no difference in ratio between the surface and solution. 14 Discussion. We have established that the ratio of coordinated Zn-TDPs over noncoordinated Zn-TDPs is higher at the ntetradecane/HOPG interface than in n-tetradecane solution.…”

Section: Scanning Tunneling Microscopy (Stm) All Experimentsmentioning

confidence: 96%

“…It also allows the analysis of mixtures of different porphyrins on a surface by comparing their relative STM contrasts, which arise from differences in their electronic properties. 14 In an example by Umezawa et al, 15 a surface sensor was described in which thiopyridine-modified STM tips were used to distinguish different metalloporphyrins. The examples above illustrate the opportunities offered by porphyrin-modified surfaces, which may provide a future basis for high density two-dimensional data storage.…”

Section: Introductionmentioning

confidence: 99%

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Two-Dimensional Molecular Patterning by Surface-Enhanced Zn-Porphyrin Coordination

et al. 2009

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Two-dimensional molecular patterning by surface-enhanced Zn-porphyrin coordination Visser, J.; Katsonis, N.; Vicario, J.; Feringa, B.L. Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. In this contribution, we show how zinc-5,10,15,20-meso-tetradodecylporphyrins (Zn-TDPs) self-assemble into stable organized arrays on the surface of graphite, thus positioning their metal center at regular distances from each other, creating a molecular pattern, while retaining the possibility to coordinate additional ligands. We also demonstrate that Zn-TDPs coordinated to 3-nitropyridine display a higher tendency to be adsorbed at the surface of highly oriented pyrolytic graphite (HOPG) than noncoordinated ones. In order to investigate the two-dimensional (2D) self-assembly of coordinated Zn-TDPs, solutions with different relative concentrations of 3-nitropyridine and Zn-TDP were prepared and deposited on the surface of HOPG. STM measurements at the liquid-solid interface reveal that the ratio of coordinated Zn-TDPs over noncoordinated Zn-TDPs is higher at the n-tetradecane/HOPG interface than in n-tetradecane solution. This enhanced binding of the axial ligand at the liquid/solid interface is likely related to the fact that physisorbed Zn-TDPs are better binding sites for nitropyridines.

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Section: Scanning Tunneling Microscopy (Stm) All Experimentsmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Two-Dimensional Molecular Patterning by Surface-Enhanced Zn-Porphyrin Coordination

et al. 2009

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“…Indeed, in total, only a few studies of SAM temperature dependence have ever been performed, as recently reviewed (12,34,35). An important conclusion drawn is that the nature of observed SAM composition can be controlled by either kinetic and/or thermodynamic effects (9,12,14,15,(33)(34)(35)(36)(37)(38)(39)(40)(41)(42)(43)(44). SAMs in thermodynamic equilibrium can have free energies determined directly from dynamics observed in the STM (17).…”

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confidence: 99%

A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers

Reimers

Panduwinata

Visser

et al. 2015

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

110

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Modern quantum chemical electronic structure methods typically applied to localized chemical bonding are developed to predict atomic structures and free energies for meso-tetraalkylporphyrin self-assembled monolayer (SAM) polymorph formation from organic solution on highly ordered pyrolytic graphite surfaces. Large polymorphdependent dispersion-induced substrate−molecule interactions (e.g., −100 kcal mol −1 to −150 kcal mol −1 for tetratrisdecylporphyrin) are found to drive SAM formation, opposed nearly completely by large polymorph-dependent dispersion-induced solvent interactions (70-110 kcal mol −1 ) and entropy effects (25-40 kcal mol −1 at 298 K) favoring dissolution. Dielectric continuum models of the solvent are used, facilitating consideration of many possible SAM polymorphs, along with quantum mechanical/molecular mechanical and dispersion-corrected density functional theory calculations. These predict and interpret newly measured and existing high-resolution scanning tunnelling microscopy images of SAM structure, rationalizing polymorph formation conditions. A wide range of molecular condensed matter properties at room temperature now appear suitable for prediction and analysis using electronic structure calculations.self-assembled monolayers | density functional theory | dispersion | free energy | polymorphism A priori calculations of the free energies of chemical reactions using density functional theory (DFT) and/or ab initio methods are now well established for gas-phase processes (1, 2), gas surface reactions (3), and, using continuum self-consistent reaction field (SCRF) methods, for condensed phase processes also (4). Over the last few years, a major advance in computational methods has occurred, however, allowing for rapid and accurate evaluation of intermolecular dispersion interactions. This makes feasible similar SCRF calculations for physisorption, macromolecule structuring, and other self-assembly processes in condensed phases. We present the first application of this type, to our knowledge, considering the free energy of formation of various polymorphs of tetraalkylporphyrin self-assembled monolayers (SAMs) at solid/liquid interfaces on highly ordered pyrolytic graphite (HOPG) surfaces. Calculated structures and free energies are used to interpret new and existing high-resolution scanning tunneling microscopy (STM) images, focusing on the critical roles played by the dispersion interaction in driving SAM formation and by entropy and dispersion-based desolvation effects that oppose it.Calculating a priori free energies for SAM formation from solution is a significant challenge. Accurate representations of the substrate−molecule energies, the intermolecular energies, the solvent interaction energies, and the effects of solvent structure are required, a set of tasks that, with a few exceptions (see e.g., refs. 5 and 6), has remained prohibitive a priori. Alternatively, model calculations have been useful for identifying key qualitative features (7-11), whereas some full molecular dynamics si...

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“…Shimizu and co-workers [104] also investigated the assembly of 3D coordinated porphyrins on HOPG surfaces. Four related porphyrins, bearing long alkoxy chains, were investigated (Fig.…”

Section: Towards the 3rd Dimension: From Structures To Functionalitymentioning

confidence: 99%

Supramolecular architectures of porphyrins on surfaces: The structural evolution from 1D to 2D to 3D to devices

Mohnani

Bonifazi

2010

Coordination Chemistry Reviews

169

134

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STM Observation of Alkyl-Chain-Assisted Self-Assembled Monolayers of Pyridine-Coordinated Porphyrin Rhodium Chlorides

Cited by 71 publications

References 80 publications

Two-Dimensional Molecular Patterning by Surface-Enhanced Zn-Porphyrin Coordination

Two-Dimensional Molecular Patterning by Surface-Enhanced Zn-Porphyrin Coordination

A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers

Supramolecular architectures of porphyrins on surfaces: The structural evolution from 1D to 2D to 3D to devices

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