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We report the synthesis of tungsten diselenide (WSe2) flakes and continuous layers using an atmospheric pressure thermally assisted conversion (TAC) method, where the tungsten (W) layers were pre-deposited by a magnetron sputtering system onto fused silica substrates. Optical microscopy (OM) and atomic force microscopy (AFM) mapping predominantly revealed the formation of isolated flakes with different shapes, mainly concentrated near the substrate’s edges, which tended to form clusters and to further overlap to continuous layers, moving to the central part of the fused silica substrates. Raman spectroscopy and photoluminescence measurements confirmed the existence of atomically thin flakes and 2H-WSe2 continuous layers. The measured current–voltage characteristics indicated Ohmic behavior under dark conditions and photo illumination. Finally, the demonstrated resistor-like behavior suggested unlimited prospects for WSe2 integration into a variety of heterostructures.

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.

Platinum diselenide (PtSe2) as a part of 2D noble transition metal dichalcogenides (nTMDCs) offer diverse optoelectronic properties which can be effectively controlled as number of layers and engineered for novel applications. In this context, our study is focused on structural and compositional characteristics of large area synthesized PtSe2 ultrathin films. In addition, optical properties analysis as a way to track the quality of PtSe2 at different synthesized stages using thermal assisted conversion (TAC) of chemical vapor deposition (CVD) was performed.

In this paper we report on the synthesis details of WSe2 nanolayers by thermally assisted selenization method of pre-deposited tungsten films in Chemical Vapour Deposition (CVD) reactor. Optical microscopy reveals WSe2 domains uniformly distributed with predominantly triangular shapes. Raman spectroscopy as well as UV-VIS-NIR spectrophotometry and sheet resistance measurements are used for characterization of the obtained 2D WSe2.

Four benzothiazolium crown ether-containing styryl dyes were prepared through an optimized synthetic procedure. Two of the dyes (4b and 4d) having substituents in the 5-position of the benzothiazole ring are newly synthesized compounds. They demonstrated a higher degree of trans–cis photoisomerization and a longer life time of the higher energy forms in comparison with the known analogs. The chemical structures of all dyes in the series were characterized by NMR, UV–vis, IR spectroscopy and elemental analysis. The steady-state photophysical properties of the dyes were elucidated. The stability constants of metal complexes were determined and are in good agreement with the literature data for reference dyes. The temporal evolution of trans-to-cis isomerization was observed in a real-time regime. The dyes demonstrated a low intrinsic fluorescence of their Ba2+ complexes and high yield of E/Z photoisomerization with lifetimes of the higher energy form longer than 500 seconds. Density functional theory (DFT) calculations at the B3LYP/6-31+G(d,p) level were performed in order to predict the enthalpies (H) of the cis and trans isomers and the storage energies (ΔH) for the systems studied.

The nucleic acids staining ability of a series asymmetric monomeric monomethine cyanine dyes prepared by simple and reliable synthetic procedure is demonstrated. The dyes show ratiometric red shift of their longer wavelength absorption maxima. It is in the range 514–522 nm neat in TE buffer, 516–528 nm in the presence of DNA, and 518–524 nm in the presence of RNA. Practically the target dyes are not fluorescent in water solutions or possess negligible fluorescence, but become strongly fluorescent after contacting with nucleic acids. A considerable increase of the fluorescence intensity upon binding to RNA compared to dsDNA is observed particularly in the group of chlorine substituted analogues 1a-1c. The intensive ICD signal of dye 1a in the presence of RNA unequivocally proves that finding. Molecular docking studies have been performed to investigate the nature of binding mode of the dyes with DNA. 1a-1c are groove binders and 2b-2c are interacting with DNA through partial intercalation mode. The nature of electronic transitions and their manifestation in the electronic spectra are revealed by DFT and TDDFT calculations.

A new modified calix[4]arene, namely 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis[(tetramethyldiamidophosphinyl)oxy]calix[4]arene (L) has been prepared by reacting the parent calixarene with tetramethyldiamidophosphoric acid chloride, and its structure was solved by the X-ray diffraction method in the solid state and characterized in solution using 1H, 13C, 31P NMR and mass spectral (ES-MS and FAB-MS) data. The coordination ability of L towards Na+ showed the formation of two different complex species, [NaL]+[AuCl4]− · 4H2O (1) and [Na2L2](ClO4)2 · (CH3OH)4 (2), depending on the reaction conditions and nature of the counter ion. Complex 1 is structurally characterized using NMR (1H, 13C, 31P) and mass spectral data. Complex 2 crystallizes with four molecules of methanol, two of them being bridges between two calixarene units and its structure was determined by X-ray analysis.

We have investigated the doping mechanism of pentacene with iodine and its impact on the structure and on the electronic properties of single crystals, powders, and thin films in a large range of iodine concentration up to six iodine per pentacene (PEN) molecule (I/PEN = 6). Three regimes of doping have been identified. In the low doping regime I/PEN < 0.05, the pristine pentacene structure of single crystals is maintained. Electron spin resonance (ESR) evidences a Pauli susceptibility, that is, the characteristic fingerprint of delocalized holes in the valence band of pentacene. In the intermediate doping regime (0.1 < I/PEN + cations and related species, for example, cation dimers (PEN+)2 and typical Raman signatures of the I3- and I5- species. Spin pairing of pentacene cation radicals is further supported by the observation of a thermally activated behavior of the ESR spin susceptibility. In the heavy doping regime (2 < I/PEN

Reference LCSL-ARTICLE-2004-013View record in Web of Science Record created on 2006-02-15, modified on 2017-05-12

Two members of the tetradentate N-donor ligand families 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe4-BTPhen 2 has faster complexation kinetics than CyMe4-BTBP 1. The values for the HOMO-LUMO gap of 2 are comparable with those of CyMe4-BTBP 1 for which the HOMO-LUMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex ≥ heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped-flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol(-1)) energy barrier to rotation about the central biaryl C-C axis in order to achieve the cis-cis conformation that is required to form a complex, whereas the cis-cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe4-BTPhen 2 with Y(NO3)3 is also reported. The metal ion is 10-coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)°, 6.4(2)°, 9.7(2)°, respectively.

The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-2,2′ : 6′,2′′-terpyridine (CyMe4-hemi-BTBP) has been synthesized and its interactions with Am(III), U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UV absorption spectrophotometry, NMR studies and ESI-MS. Structures of 1 : 1 complexes with Eu(III), Ce(III) and the linear uranyl (UO22+) ion were obtained by X-ray crystallographic analysis, and they showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III) complex is higher. 1H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1 : 1 complexes with Eu(III), Ce(III) and Yb(III), while both 1 : 1 and 1 : 2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2 : 2 helical complexes was formed with Cu(I), with a slight preference (1.4 : 1) for a single directional isomer. In contrast, a 1 : 1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III) from Ln(III) by quadridentate N-donor ligands.

A method for the synthesis of Gly, Ala, Phe, and Thr esters is proposed and considered as being a stage of possible biomimetic synthesis of peptides. The methyl esters of the said amino acids are obtained via intervention of 2-hydroxypropyl phosphonate. The resulting aminoacyl phosphonates reacts with methanol to produce the amino acid methyl esters, with the release of phosphoric acid. The reaction is carried out at room temperature in water. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:252–255, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20427

A series of bis-iminonitroxide diradical derivatives of different lengths and geometry have been prepared that incorporate a conjugated phenylene-ethynylene bridge as a rigid spacer. This paper describes the synthesis of these new components and their main characterizations. An unexpected singlet ground state and substituent effects on the singlet-triplet gap have been found for substituted "m-phenylene"-based diradicals. The effects of the pi-conjugation on the intramolecular through-bond spin coupling have been investigated by changing the length of the spacer within linear derivatives. The EPR studies demonstrate the intramolecular magnetic coupling between the radical spins within all compounds. This result is very attractive and unusual, given the large distance between the radicals from 15 A in the dimer to 36 A in the pentamer.