X-ray Photoelectron Spectroscopy and Near-Edge X-ray Absorption Fine Structure Study of Water Adsorption on Pyridine-Terminated Thiolate Self-Assembled Monolayers

Zubavichus, Yan V.; Zharnikov, Michael; Yang, Yongjie; Fuchs, O.; Umbach, E.; Heske, Clemens; Ulman, A.; Grunze, M.

doi:10.1021/la047980b

Cited by 68 publications

(131 citation statements)

References 31 publications

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“…Such a shift has been observed in pyridine-terminated SAMs on Au substrates, in which the C 1s emissions related to the carbon atoms in the ortho and para positions of the pyridine were observed at 285.3-286.6 eV. [42] A single emission in the N 1s spectrum related to nitrogen atom incorporation into the aromatic rings is observed at a BE of 399.0 eV for both PPPT/Au and PPPT/Ag. This BE is very close to the value expected for an unmodified pyridine moiety (ca.…”

Section: Xps and Nexafs Characterizationmentioning

confidence: 62%

Charge Transport through Oligoarylene Self‐assembled Monolayers: Interplay of Molecular Organization, Metal–Molecule Interactions, and Electronic Structure

Grave¹,

Risko²,

Shaporenko

et al. 2007

Adv Funct Materials

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The electrical properties of two molecular wires?a novel aryl moiety, 6‐(5‐pyridin‐2‐ylpyrazin‐2‐yl)pyridine‐3‐thiol (PPPT), and the well studied 1,1';4',1''‐terphenyl‐4‐thiol (TPT)?organized in self‐assembled monolayers (SAMs) are measured using metal–molecule–metal (MMM) mercury‐drop junctions. Current measured at the same bias voltage through PPPT is found to be more than one order of magnitude lower than through TPT. To interpret and understand these results, characterization of the structure, organization of the SAMs, and theoretical analyses of the molecular systems are discussed. X‐ray photoelectron spectroscopy (XPS) and near‐edge X‐ray absorption fine structure spectroscopy (NEXAFS) indicate that although PPPT forms high‐quality SAMs on both Au and Ag substrates, it exhibits a lower packing density (by 20 %) and less orientational order than TPT. In addition, electronic structure calculations with density functional theory (DFT) reveal that the electron‐withdrawing nitrogen atoms in the PPPT aryl backbone stabilize the valence molecular electronic structure and pull negative charge from the thiol sulfur. This behavior can influence both charge‐injection barriers and metal–molecule binding interactions in the MMM junctions. The current–voltage data are interpreted on the basis of a hole‐tunneling, through‐bond mechanism. Conductance analysis through a model for off‐resonant tunneling transport suggests that a comparatively small difference in the charge‐injection barrier can explain the factor of ten difference in observed conduction.

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Section: Xps and Nexafs Characterizationmentioning

confidence: 62%

Charge Transport through Oligoarylene Self‐assembled Monolayers: Interplay of Molecular Organization, Metal–Molecule Interactions, and Electronic Structure

Grave¹,

Risko²,

Shaporenko

et al. 2007

Adv Funct Materials

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“…Monte Carlo simulations and sum frequency generation (SFG) experiments have shown that hydrogen bonding to oxygen atoms of oligo(ethylene glycol)-terminated SAMs [31,32]. Pyridine-terminated SAMs are strongly affected by water adsorption where H bonding and partial proton transfer was observed [33].…”

Section: Discussionmentioning

confidence: 99%

In situphotoelectron spectroscopy study of water adsorption on model biomaterial surfaces

Ketteler

Ashby

Mun

et al. 2008

J. Phys.: Condens. Matter

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Abstract. Using in situ photoelectron spectroscopy at near ambient conditions, we compare the interaction of water with four different model biomaterial surfaces: self-assembled thiol monolayers on Au(111) that are functionalized with methyl, hydroxyl, and carboxyl groups, and phosphatidylcholine (POPC) lipid films on Silicon. We show that the interaction of water with biomaterial surfaces is mediated by polar functional groups that interact strongly with water molecules through hydrogen bonding, resulting in adsorption of 0.2-0.3 ML water on the polar thiol films in 700 mTorr water pressure and resulting in characteristic N1s and P2p shifts for the POPC films. Provided that beam damage is carefully controlled, in situ electron spectroscopy can give valuable information about water adsorption which is not accessible under ultra-high vacuum conditions.

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“…5B) is indicative of a single species and suggests that the complex adsorbs intact. The binding energy indicates an iron(II) species [65], as inferred from comparison with other complexes where the iron(II) ion is coordinated to nitrogen ligands, such as phthalocyanines or porphyrins [66,67]. That the complex adsorbs intact may also be inferred from the nitrogen signal, whose intensity is close to the stoichiometric ratio.…”

Section: X-ray Photoelectron Spectroscopy (Xps)mentioning

confidence: 93%

Thiocyanate Anchors for Salt-like Iron(II) Complexes on Au(111): Promises and Caveats

Stock

Erbe

Buck

et al. 2014

Zeitschrift Für Naturforschung B

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The formation of self-assembled monolayers (SAMs) on Au(111) from solution has been investigated for two ionic iron(II) complexes of the type [Fe(L)](BF 4 ) 2 , where L is tripodal hexadentate and contains three thiocyanate anchor groups. The ligands (L1, L2; donor set: N 6 ) are obtained by Schiff base condensation of a tripodal triamine (L1: tris-(2-aminoethyl)amine, 'tren'; L2: 1,1 ,1 -trimethyl(thiophosphoryl)trihydrazide) with 5-(4-thiocyanatobutoxy) pyridine-2-carbaldehyde. Layers of the complexes adsorbed on Au(111) from methanol solution have been characterised using scanning tunnelling microscopy (STM), infrared reflectance absorbance (IRRAS), X-ray photoelectron (XPS) and UV/Vis reflectance spectroscopies, as well as ellipsometry. Complex [Fe(L1)](BF 4 ) 2 deposits intact on a gold surface and retains its optical addressability. Elaboration of this result may provide access to a new class of self-assembled layers, employing salt-like tripodal coordination compounds with thiocyanate anchors. The second complex, [Fe(L2)](BF 4 ) 2 , which contains a sulphur atom in the ligand backbone, is not sufficiently stable under the same conditions.

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X-ray Photoelectron Spectroscopy and Near-Edge X-ray Absorption Fine Structure Study of Water Adsorption on Pyridine-Terminated Thiolate Self-Assembled Monolayers

Cited by 68 publications

References 31 publications

Charge Transport through Oligoarylene Self‐assembled Monolayers: Interplay of Molecular Organization, Metal–Molecule Interactions, and Electronic Structure

Charge Transport through Oligoarylene Self‐assembled Monolayers: Interplay of Molecular Organization, Metal–Molecule Interactions, and Electronic Structure

In situphotoelectron spectroscopy study of water adsorption on model biomaterial surfaces

Thiocyanate Anchors for Salt-like Iron(II) Complexes on Au(111): Promises and Caveats

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