Polarized NEXAFS Spectroscopic Studies of Poly(butylene terephthalate), Poly(ethylene terephthalate), and Their Model Compounds

Okajima, Toshihiro; Teramoto, Kazuyoshi; Mitsumoto, R.; Oji, Hiroshi; Yamämoto, Yasushi; Mori, Isamu; Ishii, Hisao; Ouchi, Yukio; Seki, Kazuhiko

doi:10.1021/jp981164t

Cited by 46 publications

(41 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…47,69 For the C K-edge, all spectra contain a dominant resonance from transitions into the π* orbital of the phenyl rings at 285.0 eV (π* Ph ) and into the π* orbital of the COOH/COO-groups at ~288.5 eV (π* COOH ).…”

Section: Methodsmentioning

confidence: 99%

Self-Assembled Monolayers of Oligophenylenecarboxylic Acids on Silver Formed at the Liquid–Solid Interface

et al. 2016

View full text Add to dashboard Cite

A series of para-oligophenylene mono-and dicarboxylic acids (R-(C 6 H 4 ) n COOH, n=1-3, R=H,COOH) was studied. Adsorbed on Au(111)/mica modified by an underpotential deposited bilayer of Ag, the self-assembled monolayers (SAMs) were analysed by near edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy and scanning tunneling microscopy. In all cases SAMs are formed with molecules adopting an upright orientation and anchored to the substrate by a carboxylate. Except benzoic acid, all SAMs could be imaged at molecular resolution, which revealed highly crystalline layers with a dense molecular packing. The structures of the SAMs are described by a rectangular (5×√3) unit cell for the prevailing phase of the monocarboxylic acids and an oblique (√93×√133) unit cell for the dicarboxylic acids, thus, evidencing a pronounced influence of the second COOH moiety on the SAM structure. Density functional theory calculations suggest that hydrogen bonding between the SAM terminating COOH moieties accounts for the difference. Contrasting other classes of SAMs, the systems studied here are determined by intermolecular interactions whereas molecule-substrate interactions play a secondary role. Thus, eliminating problems arising from the mismatch between the molecular and substrate lattices, coordinatively bonded carboxylic acids on silver should provide considerable flexibility in the design of SAM structures.

show abstract

Section: Methodsmentioning

confidence: 99%

Self-Assembled Monolayers of Oligophenylenecarboxylic Acids on Silver Formed at the Liquid–Solid Interface

et al. 2016

View full text Add to dashboard Cite

show abstract

“…28 The energy calibration was performed with a spectrum of hexatriacontane (n-C36H74), where the main peak assigned to the σ*(C-H) transition is located at 287.8 eV. 29 In order to estimate the tilt angle of molecules, we measured spectra at 5 or 3 different angles for THT and TP SAMs, respectively. Figure 2 show the surface structures of THT and TP SAMs on Au(111) formed after immersion of the Au(111) substrates in a 1 mM ethanol solution at RT for 24 h. STM imaging with molecular-level resolution reveals that the adsorption of THT and TP molecules on Au(111) leads to the formation of well-ordered SAMs with unique domain structures, as shown in Figure 2.…”

Section: Methodsmentioning

confidence: 99%

Comparative Study of Tetrahydrothiophene and Thiophene Self Assembled Monolayers on Au(111): Structure and Molecular Orientation

2009

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

Surface structure and molecular orientation of self-assembled monolayers (SAMs) formed by the spontaneous adsorption of tetrahydrothiophene (THT) and thiophene (TP) on Au(111) were investigated by means of scanning tunneling microscopy (STM) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy. STM imaging revealed that THT SAMs have a commensurate (3 × 2√3) structure containing structural defects in ordered domains, whereas TP SAMs are composed of randomly adsorbed domains and paired molecular row domains that can be described as an incommensurate packing structure. The NEXAFS spectroscopy study showed that the average tilt angle of the aliphatic THT ring and π-conjugated TP ring in the SAMs were calculated to be about 30 o and 40 o , respectively, from the surface normal. It was also observed that the π* transition peak in the NEXAFS spectrum of the TP SAMs is very weak, suggesting that a strong interaction between π-electrons and the Au surface arises during the self-assembly of TP molecules. In this study, we have clearly demonstrated that the surface structure and adsorption orientation of organic SAMs on Au(111) are strongly influenced by whether the cyclic ring is saturated or unsaturated.

show abstract

“…Eight peaks have been labeled in the figure: A, B, C, D, and E ͑at BEs of 284.9, 285.5, 286.8, 288.3, and 290.2 eV, respectively͒ were assigned to C 1s → * transitions and F, G, and H ͑at BEs of around 293.2, 297.7, and 301 eV, respectively͒ to C 1s → * transitions. 33 The set of spectra shows a clear dependence of the peak intensities. In particular, the pronounced dichroism of peaks A and B, which are related to the phenyl ring, and of peak D, which is connected to the carbonyl group, indicates almost flat lying molecules.…”

Section: -3mentioning

confidence: 95%

Coexistence of one- and two-dimensional supramolecular assemblies of terephthalic acid on Pd(111) due to self-limiting deprotonation

Cañas‐Ventura

Klappenberger

Clair

et al. 2006

The Journal of Chemical Physics

View full text Add to dashboard Cite

The adsorption of terephthalic acid ͓C 6 H 4 ͑COOH͒ 2 , TPA͔ on a Pd͑111͒ surface has been investigated by means of scanning tunneling microscopy ͑STM͒, x-ray photoelectron spectroscopy, and near-edge x-ray absorption fine structure spectroscopy under ultrahigh vacuum conditions at room temperature. We find the coexistence of one-͑1D͒ and two-dimensional ͑2D͒ molecular ordering. Our analysis indicates that the 1D phase consists of intact TPA chains stabilized by a dimerization of the self-complementary carboxyl groups, whereas in the 2D phase, consisting of deprotonated entities, the molecules form lateral ionic hydrogen bonds. The supramolecular growth dynamics and the resulting structures are explained by a self-limiting deprotonation process mediated by the catalytic activity of the Pd surface. Our models for the molecular ordering are supported by molecular mechanics calculations and a simulation of high resolution STM images.

show abstract

Polarized NEXAFS Spectroscopic Studies of Poly(butylene terephthalate), Poly(ethylene terephthalate), and Their Model Compounds

Cited by 46 publications

References 36 publications

Self-Assembled Monolayers of Oligophenylenecarboxylic Acids on Silver Formed at the Liquid–Solid Interface

Self-Assembled Monolayers of Oligophenylenecarboxylic Acids on Silver Formed at the Liquid–Solid Interface

Comparative Study of Tetrahydrothiophene and Thiophene Self Assembled Monolayers on Au(111): Structure and Molecular Orientation

Coexistence of one- and two-dimensional supramolecular assemblies of terephthalic acid on Pd(111) due to self-limiting deprotonation

Contact Info

Product

Resources

About