Arrays of Double-Decker Porphyrins on Highly Oriented Pyrolytic Graphite

Otsuki, Joe; Kawaguchi, Satoru; Yamakawa, Toshihisa; Asakawa, Masumi; Miyake, Koji

doi:10.1021/la0608617

Cited by 73 publications

(61 citation statements)

References 47 publications

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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).…”

mentioning

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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mentioning

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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“…These sandwich structures provide rotational degrees of freedom, where the top molecular plane (rotor) is able to rotate with respect to the bottom one (stator) that is anchored on the surface. [11,12] These large double-and triple-decker molecules are generally susceptible to thermal decomposition and often unsuitable for high-temperature vapor deposition, indeed, only a few examples are reported. [13,14] Alternatively, observations are possible at solid/liquid interfaces in an insulating organic solvent [12,15] or under electrochemical control in an electrolyte solution.…”

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confidence: 99%

Assembly and Manipulation of Rotatable Cerium Porphyrinato Sandwich Complexes on a Surface

et al. 2011

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“…Among them, porphyrins and phtalocyanins are already known to self-organize into well-ordered structures on clean graphite surfaces [44]. When deposited on hole doped graphene, these molecules act as donors and electron-dope the pristine substrate.…”

Section: Adatoms Agregates or Moleculesmentioning

confidence: 99%

Quantum Transport in Graphene: Impurity Scattering as a Probe of the Dirac Spectrum

Guéron

Bouchiat

2017

Progress in Mathematical Physics

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Abstract. Since the very first investigations of the electronic properties of graphene, the nature of the scattering disorder potential has been shown to play an essential role in determining the carrier density dependence of the conductance. Impurity scattering is characterized by two different times the transport and elastic scattering times which are sensitive to the particular Dirac spectrum of graphene. The analysis of the ratio between these two times gives insight on the nature (neutral or charged) and range of the scatterers. We show how to extract these two times from magneto-transport measurements and analyze their differences in monolayer and bilayer Graphene in relation with the different symmetry properties of their band structure and wave functions. It is found that whereas short range impurity scattering is the dominant mechanism limiting the classical transport, phase coherent mesoscopic transport is very sensitive to long range disorder. In particular, the formation of electron/hole puddles in the vicinity of the charge neutrality point strongly affects the transport of Andreev pairs in the presence of superconducting electrodes. We will also discuss the modification of electronic properties of graphene in the presence of adsorbed atoms and molecules and in particular focus on spin dependent scattering on adsorbates leading to a spin orbit interaction. There is indeed a big interest in controlling and inducing spin orbit interactions in graphene. One can hope to induce and detect a spin Hall effect with a great potential impact in graphene based spintronic devices and ultimately reach a regime of quantum spin Hall physics. In contrast with these very short range scatterers, we discuss the possibility to engineer networks of larger range strained regions in which electronic properties are locally modified by transferring graphene on arrays of silicon oxyde nanopillars.

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Arrays of Double-Decker Porphyrins on Highly Oriented Pyrolytic Graphite

Cited by 73 publications

References 47 publications

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

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

Assembly and Manipulation of Rotatable Cerium Porphyrinato Sandwich Complexes on a Surface

Quantum Transport in Graphene: Impurity Scattering as a Probe of the Dirac Spectrum

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