Perylene-3,4,9,10-tetracarboxylic Acid Dianhydride Research Articles

White Light Generation from a Self-Assembled Fluorogen-Surfactant Composite Light Harvesting Platform.

Nonionic surfactant modulated aggregation induced emission enhancement (AIEE) of Dimethyl-2,5-bis(4-(methoxyphenyl)amino)terephthalate (DBMPT) has been investigated. DBMPT exhibits unidirectional aggregated growth with nonionic triton X-100 (TX-100) to produce highly luminescent nanorods, the dimensions and emission intensities of which are controlled by concentration of DBMPT. Energy transfer from perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTAD) to these nanorods in aqueous medium produces pure white light emission with the CIE chromaticity coordinates (0.33, 0.36) and a significantly high quantum yield of 35%. Gelation of the system with agarose yields a bright white light emitting gel. Both these factors demonstrate an excellent potential for application of this system in light harvesting and as an advanced material for organic electronic devices.

Inhomogeneous and Homogeneous Line Broadening of Optical Spectra of PTCDA Molecules Adsorbed at Step Edges of Alkali Halide Surfaces

We report a detailed analysis of the line shapes of the 0–0 transitions in the fluorescence (FL) and fluorescence excitation (FLE) spectra of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) molecules adsorbed at terrace and step edge sites of (100)-oriented alkali halide films (KCl and NaCl). At low temperatures (6–20 K), we find very narrow FLE lines with a fwhm of 4.5 cm–1 (3.0 cm–1) on KCl (NaCl). These line shapes are dominated by inhomogeneous broadening related to the structural variation of the environment of the PTCDA molecules. We explain this site broadening on the basis of structural models for the adsorption sites at the step edges from earlier scanning microscopy data and density functional theory calculations. With increasing temperatures, the 0–0 lines in the FL and FLE spectra broaden; e.g., in the FL, the fwhm increases to 26 cm–1 (18 cm–1) at 100 K on the KCl (NaCl) surface. This temperature induced broadening is of Lorentzian shape and can be described by the theory of Hsu an...

Surface induced vibrational modes in the fluorescence spectra of PTCDA adsorbed on the KCl(100) and NaCl(100) surfaces.

We report a combined experiment-theory study on low energy vibrational modes in fluorescence spectra of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) molecules. Using very low coverages, isolated molecules were adsorbed on terrace sites or at sites located at residual steps on (100) oriented alkali halide films (KCl and NaCl). The low energy modes couple to the optical transition only because the PTCDA molecule is geometrically distorted (C2v) upon adsorption on the surface; they would be absent for the parent planar (D2h) PTCDA molecule. The modes differ in number and energy for molecules adsorbed on regular terrace sites and molecules adsorbed at step edge sites. Modes appearing for step edge sites have the character of frustrated rotations. Their coupling to the optical transition is a consequence of the further reduced symmetry of the step edge sites. We find a larger number of vibrational modes on NaCl than on KCl. We explain this by the stronger electrostatic bonding of the PTCDA on NaCl compared to KCl. It causes the optical transition to induce stronger changes in the molecular coordinates, thus leading to larger Franck-Condon factors and thus stronger coupling. Our results demonstrate how optical spectroscopy can be used to gain information on adsorption sites of molecules at low surface concentrations.

Synthesis and properties of amino acid functionalized water-soluble perylene diimides

We prepared amino acid functionalized water-soluble perylene diimides: N,N′-bi(L-glutamic acid)-perylene-3,4;9,10-dicarboxylic diimide (1), N,N′-bi(L-phenylalanine acid)-perylene-3,4;9,10-dicarboxylic diimide (2), N,N′-bi(L-glutamic amine)-perylene-3,4;9,10-dicarboxylic diimide (3) and N,N′-bi(L-phenylalanine amine)-perylene-3,4;9,10-dicarboxylic diimide (4). The structures of 3 and 4 were confirmed by 1H NMR, FT-IR and MS. The maximal absorption bands of compound 1 and 2 in concentrated sulfuric acid were red-shifted for about 48 and 74 nm, respectively, compared with that of Perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA). Nearly no fluorescence was observed for compounds 1 and 2 in water, while compounds 3 and 4 were significantly water-soluble and had very high fluorescent quantum. The mechanism of the optical properties change was discussed, and the π-π stacking caused by H+ led to the changes of fluorescence spectrum and absorption spectrum. The calculated molecular orbital energies and the frontier molecular orbital maps of compounds 1–2 based on density function theory (DFT) calculations were reported. Owing to the high water-soluble, the perylene derivatives 3 and 4 were successfully applied as high-performance fluorochromes for living hela cells imaging.

Lateral ordering of PTCDA on the clean and the oxygen pre-covered Cu(100) surface investigated by scanning tunneling microscopy and low energy electron diffraction.

We have investigated the adsorption of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) on the clean and on the oxygen pre-covered Cu(100) surface [referred to as (√2 × 2√2)R45° – 2O/Cu(100)] by scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). Our results confirm the (4√2 × 5√2)R45° superstructure of PTCDA/Cu(100) reported by A. Schmidt et al. [J. Phys. Chem. 1995, 99,11770–11779]. However, contrary to Schmidt et al., we have no indication for a dissociation of the PTCDA upon adsorption, and we propose a detailed structure model with two intact PTCDA molecules within the unit cell. Domains of high lateral order are obtained, if the deposition is performed at 400 K. For deposition at room temperature, a significant density of nucleation defects is found pointing to a strong interaction of PTCDA with Cu(100). Quite differently, after preadsorption of oxygen and formation of the (√2 × 2√2)R45° – 2O/Cu(100) superstructure on Cu(100), PTCDA forms an incommensurate monolayer with a structure that corresponds well to that of PTCDA bulk lattice planes.

A fluorescent perylene-assembled polyvinylpyrrolidone film: synthesis, morphology and nanostructure

A fluorescent polyvinylpyrrolidone (PVP) film with assembled nanostructures is successfully prepared in one pot by using perylene-3,4,9,10-tetracarboxylic acid dianhydride (PDA) as the fluorophore. The reactive anhydride groups in PDA play an important role in the covalent bonding of fluorescent molecules in the fluorescent PVP film, which has been demonstrated by a small-molecule model reaction. Interestingly, rod-like structures are found on the surface of the fluorescent film, which is attributed to the π-π interaction of PDA that occurred in the crosslinked PVP film. Further polarized optical microscopy (POM), X-ray diffraction (XRD) and optical analyses demonstrate the stable existence of π-conjugated nanostructures in the fluorescent PDA-based PVP film. The reactive anhydrides and the π-π interaction of perylene molecules are essential for the fabrication of the fluorescent perylene-assembled PVP film. This method could be extended to the preparation of the fluorescent PVP film with self-assembled nanostructures.

Spectroscopy of isolated PTCDA molecules on the KCl(100) surface: Vibrational spectra and azimuthal orientation

Small amounts of the model molecule perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) were vacuum deposited on epitaxial KCl films on Ag(100). The use of a low substrate temperature (20 K) during deposition hampered molecular diffusion resulting in isolated monomers on the surface. Fluorescence and fluorescence excitation spectroscopy performed on these monomers yielded highly resolved spectra with narrow lines corresponding to individual vibronic modes. This high resolution in our spectra is caused by a very small inhomogeneous broadening due to well-defined adsorption sites of the molecule on the substrate. Indeed, by polarization dependent fluorescence spectroscopy we show that the flat-lying molecules exhibit a preferred azimuthal orientation on the surface, the long molecular axis being oriented along the [011] or the equivalent [011] direction of the substrate. Furthermore, the high resolution in the spectra allowed a detailed analysis of the vibronic modes. The vibrational modes of the adsorbed molecule are very similar to those of the free PTCDA molecule, but due to the presence of the substrate additional low energy modes which are relevant for the full understanding of the spectra couple to the transition.

衬底对PTCDA薄膜结构与电荷输运特性的影响

Perylene-3,4,9,10-tetracarboxylic acid dianhydride(PTCDA) thin films were vacuum evaporated on Au,Al and ITO substrates,their structure and morphology were analysed by X-ray spectroscopy(XRD) and atomic force microscope(AFM).The results show that most of PTCDA molecules don't lie parallel to the substrate,which indicates that electron transport dominates the current conduction in the direction perpendicular to the film plane.PTCDA films grown on ITO and Au arrange regularly.It shows good electronic transport properties perpendicular to the film plane.But the grains of PTCDA film grown on Al arrange disorderly resulting in poor performance of electronic conduction.By the thermionic emission theory at metal-organic interface and space charge limited current conduction theory in the organic bulk and considering the electric field effect on mobility,current density-voltage curves of ITO/PTCDA/Al devices were fitted in different PTCDA film's thickness.The numerical value of electron mobility dependent on electric field was determined for the specific PTCDA film thickness.

Angular dependent NEXAFS study of the molecular orientation of PTCDA multilayers on Au (111) surface

The molecular orientation of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) multilayers adsorbed on Au (111) surface has been investigated using angular dependent O K-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The significant angular dependence of important resonant structures (π* and σ*) reveals that PTCDA molecules adopt an ordered geometry on the substrate surface. The average tilt angle of the PTCDA molecular planes is 27°±10° from the Au (111) surface.

Structure of Epitaxial Layers of KCl on Ag(100)

We investigated the epitaxial growth of thin KCl films on Ag(100) by spot-profile-analysis low energy electron diffraction (SPA-LEED) and scanning tunnelling microscopy (STM). The structural relation of the (100)-oriented KCl film with respect to the Ag(100) surface is incommensurate, nevertheless the structural quality is very high and terraces with an average diameter of 250 Å are obtained. The unit cells of KCl and Ag(100) are aligned, and there is no rotational mosaicity as present in the case of NaCl on Ag(100). We attribute this to a small interaction between KCl and Ag(100) and growth starting at step edges of the metal substrate. In order to demonstrate the high structural quality of the KCl films, we deposited a monolayer of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) on these films. We obtained the identical monolayer structure that was observed earlier on bulk KCl. We thus suggest that KCl/Ag(100) is ideal for surface experiments on thin dielectric films.

Stable and metastable phases of PTCDA on epitaxial NaCl films on Ag(100)

Thin films of the model molecule perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) were vacuum deposited on epitaxial NaCl films on Ag(100) and investigated by spot-profile-analysis low-energy electron diffraction (SPA-LEED). At growth temperatures between 193 K and room temperature (RT), the first layer (monolayer) exhibits a commensurate $(3\sqrt{2}\ifmmode\times\else\texttimes\fi{}3\sqrt{2})R45\ifmmode^\circ\else\textdegree\fi{}$ superstructure with a quadratic unit cell, which is identical to that found for PTCDA growth on bulk NaCl crystals [Burke et al., Phys. Rev. Lett. 100, 186104 (2008)]. At RT, dewetting occurs and complicates the formation of multilayers. However, at low surface temperatures (223 K), closed PTCDA multilayers grow. The corresponding unit cell $[19.69(4)\text{ }\text{\AA{}}\ifmmode\times\else\texttimes\fi{}12.23(3)\text{ }\text{\AA{}}]$ is rectangular and similar to the herringbone structure of the (102) bulk plane of PTCDA. This growth form is metastable and the surface dewets upon annealing at 300 K. Submonolayers deposited at low temperatures (20--100 K) are disordered; upon annealing, they transform into the $(3\sqrt{2}\ifmmode\times\else\texttimes\fi{}3\sqrt{2})R45\ifmmode^\circ\else\textdegree\fi{}$ structure via a third metastable phase with a herringbone-type rectangular unit cell.

IR absorption anisotropy in perylene-3,4,9,10-tetracarboxylic acid dianhydride

Introduction. Organic semiconducting materials are currently widely employed in the production of functional instruments and devices such as organic transistors and microcircuits, solar cells, light-emitting diodes and electroluminescent displays, radio-frequency ID chips, electronic paper, etc. [1]. Semiconducting materials based on perylene derivatives, which are aromatic compounds, are some of the most common ones and are used as dyes in the textile industry. The optical and electric properties of these materials are comparable with those of inorganic broad-band semiconductors. Perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCADA) is a special base molecule among perylene derivatives. Like most perylene derivatives, materials based on PTCADA are typically anisotropic and, therefore, have anisotropic physicochemical properties. For example, the conductivity parallel and perpendicular to the orientation axis of molecular PTCADA crystallites can differ by six orders of magnitude [2]. The optical properties of PTCADA are also strongly anisotropic [3]. A study of the anisotropy of the structure and properties suggests ways of using it to fabricate functional devices based on perylene derivatives. Herein the specifics of IR absorption anisotropy in the region 700–900 cm –1 for various incident angles of radiation relative to the substrate normal are studied.

Self-Assembled Monolayers of a Bis(pyrazol-1-yl)pyridine-Substituted Thiol on Au(111)

Self-assembled monolayers (SAMs) of a bis(pyrazol-1-yl)pyridine-substituted thiol (bpp-SH) on Au (111)/mica were studied with scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Using substrates precoated with perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA), preparation at elevated temperatures yields highly ordered layers whose structure is described by a rectangular (5 x radical3) unit cell containing one molecule. The bis(pyrazol-1-yl)pyridine (bpp) units exhibit pi-stacking along the 112 direction, and they are tilted significantly. We conclude the three imine nitrogen atoms in the bpp headgroup adopt a trans,trans arrangement.

Highly ordered thin films of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) on Ag(1 0 0)

We report experiments performed on vacuum deposited perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) films on Ag(1 0 0) by spot profile analysis low energy electron diffraction (SPA-LEED) and scanning tunnelling microscopy (STM). Up to a coverage of 1 ML, PTCDA forms a commensurate c(8 × 8) structure with two molecules per primitive unit cell, which are perpendicularly oriented to each other (four molecules per c(8 × 8) unit cell). The PTCDA islands exhibit an equilibrium shape that corresponds to the symmetry of the Ag(1 0 0) surface. The structural order is stable up to a temperature of ∼670 K, at which a phase transition to a disordered phase occurs. Upon cooling back to room temperature, the order is partly re-obtained, although there is evidence that molecules have partly desorbed and dissociated at the high temperature. At coverages above 1 ML, a second layer orders in a herringbone structure on top of the c(8 × 8)-ordered first layer. The corresponding unit cell is very similar to that of the (1 0 2) plane of PTCDA bulk crystals.

Melting‐reactive dyes for mass coloration of nylon based on blend compatibilization: Perylene‐3,4,9,10‐tetracarboxylic acid dianhydride

AbstractThe mass coloration of nylon‐1010 with a melting‐reactive dye, an economically favorable and environmentally friendly method of coloration, is described. Perylene‐3,4,9,10‐tetracarboxylic acid dianhydride (PTAD) was used as a melting‐reactive dye for nylon‐1010, and it showed high thermal stability. A chain‐extending reaction was confirmed by an ultraviolet–visible spectroscopic analysis. The effect of the proportion of added PTAD on the intrinsic viscosity of the polymer was studied, and increased amounts resulted in increased intrinsic viscosity. The light fastness of the colored fibers was found to be 4. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2164–2167, 2002

Melting-reactive dyes for mass coloration of synthetic fibres—part I: perylene-3,4,9,10-tetracarboxylic acid dianhydride in poly(ethyleneterephthalate)

Mass coloration of poly(ethyleneterephthalate) (PET) by using a melt-reacting dye is described, and affords an economical favorable and environmentally friendly method of coloration. Perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTAD) was used as a melting-reactive dye in poly(ethyleneterephthalate) and showed high thermal stability. A chain-extending reaction was confirmed by UV–vis and IR spectroscopic analysis. The effect of the proportion of the added PTAD on the intrinsic viscosity of the polymer was studied, and increasing amounts resulted in increased intrinsic viscosity. The higher viscosity is beneficial to the spinning process. The light fastness of the colored fibres was as high as 7.