Palladium complexes of perylene diimides: strong fluorescence despite direct attachment of late transition metals to organic dyes

We prepared the first sigma-bonded metal complexes of widely utilized organic dyes, perylene tetracarboxylic acid diimides (PDIs). These 1,7-dipalladium PDI complexes were synthesized by C-Br oxidative addition of 1,7-dibromo-N,N'-dicyclohexyl PDI (Br2PDI) to Pd(0) phosphine complexes bearing triphenylphosphine and bischelating 1,2-bis(diphenylphosphino)ethane (dppe). The structures of Pd-PDI complexes were elucidated by single-crystal X-ray analysis. Surprisingly, despite direct attachement of two late transition metal centers, Pd-PDI systems are highly fluorescent (Phi=0.65 and 0.22 for triphenylphosphine and dppe systems, respectively). This is rationalized in terms of weak electronic interactions between the metal centers and PDI pi-system, as revealed by TD-DFT calculations.     

Role of humidity on indium and tin migration in organic photovoltaic devices

The stability of a common interface used in organic photovoltaic cells, between the transparent electrode of Indium Tin Oxide (ITO) and a buffer layer of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) is strongly influenced by the presence of humidity during processing, leading to significant migration of indium and tin species into the PEDOT:PSS layer. The interface was studied using neutral impact collision ion scattering spectroscopy (NICISS) and X-ray photoelectron spectroscopy (XPS), to determine migration of indium and tin into the polymer layer. It was found that the migration starts almost instantly after spin coating of the aqueous PEDOT:PSS solution and it reaches a saturation level within twenty four hours. The indium and tin were found always uniformly distributed over the sampling depth of almost one-third of the thickness of the PEDOT:PSS layer. Exposure to humidity following annealing resulted in the highest concentration (1.8 × 10(-3) mol cm(-3)) of indium or tin species, corresponding to about one indium or tin moiety per 4.7 monomer units in the PEDOT:PSS. The maximum bulk concentration of indium is about two orders of magnitude higher after exposure to humid conditions compared to vacuum dried conditions. XPS measurements confirm the presence of both indium and tin in the PEDOT:PSS and the formation of salts with the metal ions as cations.     

Microwave-assisted synthesis of naphthalenemonoimides and N-desymmetrized naphthalenediimides

Naphthalenemonoimides and N-desymmetrized naphthalenediimides were synthesized using a stepwise microwave-assisted protocol. The steric and electronic properties of aliphatic amines determined the outcome of the reactions, while in the amino acid series their ability to solubilize the naphthalene dianhydride starting material was crucial. Molecular modeling was used to rationalize the observed selectivity.     

Inkjet-printed thiol self-assembled monolayer structures on gold: quality control and microarray electrode fabrication

Laterally structured, self-assembled monolayers (SAMs) of different thiols (HS-R-X, R = (CH 2) 3-16, X = -CH 3, -COOH, -NH 2) on gold have been prepared by inkjet printing. The printer is a modified, low-cost desktop printer (Epson Stylus Photo R200), the ink is a 1 mM solution of the thiol in ethanol/glycerol (6:1). The quality of inkjet-printed large area SAMs obtained in this study is between that of a layer self-assembled from a thiol solution and that obtained by soft lithography, according to cyclic voltammetry, electrochemical impedance spectroscopy, scanning electrochemical microscopy (SECM), and polarization-modulated Fourier transform infrared reflection-absorption spectroscopy (PM IRRAS). For the first time, simultaneous printing of two different thiols in a single print job as an alternative to sequential printing and backfilling is demonstrated. The smallest structures consisting of conductive disks of 40 microm diameter were analyzed as single spots by SECM and as random array electrodes with different average disk-disk distance. Conductive band electrodes with variable bandwidth (300 microm to 1 cm) are presented, as well as a pH switchable band structure. As compared to stamping, inkjet printing allows for simultaneous multiple thiol printing in a single print job with the resolution limited only by the droplet size and the precision of the translation stage.     

Synthesis of highly phenylene substituted p-phenylene oligomers from pyrylium salts

A transition metal free route to phenyl substituted oligophenylenes that tolerates halogens is described.     

Scanning electrochemical microscopy study of laccase within a sol-gel processed silicate film

The enzyme p-diphenol:dioxygen oxidoreductase (laccase, EC 1.10.3.2) was isolated from Cerrena unicolor fungus and embedded in a sol-gel film obtained by acidic condensation of TMOS. The gel was cast to thin films on glass. The laccase-containing silicate films were inspected by confocal laser scanning microscopy (CLSM), scanning force microscopy (SFM) and scanning electrochemical microscopy (SECM). CLSM images in the reflection mode showed aggregates within the silicate films. SECM images in the substrate-generation/tip-collection mode using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as electron donor for laccase showed that the position of aggregates coincides with increased enzymatic activity within the silicate film. The flux from individual aggregates was detected. SECM images in the redox competition mode confirmed the assignment and could exclude that topographic features observed by CLSM and SFM could be the reason for the image contrast. SFM images showed that the aggregates partially dissolve during prolonged exposure to aqueous buffer. The experimental setup allowed following one individual aggregate over time with all three microscopic techniques which enabled the collection of complementing information on morphology and catalytic activity as well as their development over time.     

Photophysics and deactivation pathways of thymine

Combined complete active space perturbation theory (CASPT2) and multireference configuration interaction calculations with single and double excitations (MR-CISD) were performed in order to explore possible deactivation pathways of thymine after photoexcitation. Equilibrium geometries are reported together with a total of eight extremes (minima or maxima) on the crossing seam (MXS), through which such radiationless transitions may occur. Furthermore, conformational analysis allows grouping these conical intersections in five distinct types. Reaction paths were calculated connecting the S1 (1)n pi* minimum with the lowest-energy MXS of each group. Two distinct types of paths were observed, both with features that should delay the internal conversion to the ground state. This is shown to provide a possible explanation for the relatively long excited-state lifetime of thymine.     

On the <Emphasis Type="Italic">K</Emphasis>-Theory of Graph <Emphasis Type="Italic">C</Emphasis><Superscript>*</Superscript>-Algebras

We classify graph C ^*-algebras, namely, Cuntz-Krieger algebras associated to the Bass-Hashimoto edge incidence operator of a finite graph, up to strict isomorphism. This is done by a purely graph theoretical calculation of the K-theory of the C ^*-algebras and the method also provides an independent proof of the classification up to Morita equivalence and stable equivalence of such algebras, without using the boundary operator algebra. A direct relation is given between the K ₁-group of the algebra and the cycle space of the graph. We thank Jakub Byszewski for his input in Sect. 2.8. The position of the unit in K ₀( _Ч) was guessed based on some example calculations by Jannis Visser in his SCI 291 Science Laboratory at Utrecht University College.     

Existence,uniqueness and regularity of the projection onto differentiable manifolds

Annals of Global Analysis and Geometry - We investigate the maximal open domain $${\mathscr {E}}(M)$$ on which the orthogonal projection map p onto a subset $$M\subseteq {{\mathbb {R}}}^d$$ can be...