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Silver nanoparticles (AgNPs) were synthetized and employed in surface-enhanced Raman scattering measurements to study the chemical behavior when thiacloprid (Thia) interacts with the surface of Ag nanospheres (AgNSp) and Ag nanostars (AgNSt) upon excitation of the system with a 785 nm laser. Experimental results show that the deactivation of the localized surface plasmon resonance induces structural changes in Thia. When AgNSp are used, it is possible to observe a mesomeric effect in the cyanamide moiety. On the other hand, when AgNSt are employed, it promotes the cleavage of the methylene (-CH2-) bridge in Thia to produce two molecular fragments. To support these results, theoretical calculations based on topological parameters described by the atoms in molecules theory, Laplacian of the electron density at the bond critical point (∇2ρ BCP), Laplacian bond order, and bond dissociation energies were made, confirming that the bond cleavage is centered at the -CH2- bridge in Thia.
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A new benzotrithiophene-based small molecule, namely 2,5,8-Tris[5-(2,2-dicyanovinyl)-2-thienyl]-benzo[1,2-b:3,4-b':6,5-bâ³]-trithiophene (DCVT-BTT), was successfully synthesized and subsequently characterized. This compound was found to present an intense absorption band at a wavelength position of â¼544 nm and displayed potentially relevant optoelectronic properties for photovoltaic devices. Theoretical studies demonstrated an interesting behavior of charge transport as electron donor (hole-transporting) active material for heterojunction cells. A preliminary study of small-molecule organic solar cells based on DCVT-BTT (as the P-type organic semiconductor) and phenyl-C61-butyric acid methyl ester (as the N-type organic semiconductor) exhibited a power conversion efficiency of 2.04% at a donor: acceptor weight ratio of 1:1.
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Solvatochromic dyes are utilized in various chemical and biological media as chemical sensors. Unfortunately, there is no simple way to predict the type of solvatochromism based on the structure of the dye alone, which restricts their design and synthesis. The most important family of solvatochromic sensors, pyridinium phenolate dyes, has the strongest solvatochromism. Using a natural population analysis (NPA) of the natural bond orbitals (NBO) of the phenolate group in the frontier molecular orbitals, it is possible to calculate the relative polarity of the ground state and excited state and, thus to develop a model that can predict the three types of solvatochromism observed for this family: negative, positive, and inverted. This methodology has been applied to thirteen representative examples from the literature. Our results demonstrate that the difference in the electron density of the phenolate moiety in the frontier molecular orbitals is a simple and inexpensive theoretical indicator for calculating the relative polarity of the ground and excited states of a representative library of pyridinium phenolate sensors, and thus predicting their solvatochromism. Comparing the results with the bond length alternation (BLA) and bond order alternation (BOA) indices showed that the NPA/NBO method is a better way to predict solvatochromic behavior.
Assuntos
Corantes , Corantes/químicaRESUMO
Three photobicyclized benzodithienoquinolizinium tetrafluoroborates (BPDTQBF4) were prepared and evaluated by UV-Vis and fluorescence spectral, electrochemical analysis, and by theoretical calculations as possible organic n-type semiconductors. Evaluation and comparison of their LUMO levels, HOMO-LUMO energy gaps as monomeric and π-stacked dimers with those of other materials, suggest their potential as organic n-type semiconductors. Calculations of their relative charge carrier mobilities confirmed this potential for one derivative with a long (C-14) alkyl chain appended to the polycyclic planar π-system.
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The thermohalochromic behavior of Reichardt's E(T)(30) betaine - the temperature-dependent variation of its halochromic band in the presence of a cation - was investigated for the first time in NaI solutions of HBD- (methanol, ethanol, 1-propanol, 1-butanol) and non-HBD-solvents (acetonitrile, dimethylformamide) at 15 and 55 °C. The solvent-dependent thermohalochromism of the pyridinium-N-phenolate betaine dye was interpreted in terms of the effect of the temperature on the dye-cation association in solution.
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Betaína/química , Corantes/química , Fenóis/química , Compostos de Piridínio/química , Solventes/química , TemperaturaRESUMO
Infrared and Raman spectra of O,O-dimethyl S-methylcarbamoylmethylphosphorodithioate, dimethoate, have been recorded. Density functional theory, DFT, with the B3LYP functional was used for the optimization of the ground state geometry and simulation of the infrared and Raman spectra of this molecule. Calculated geometrical parameters fit very well with the experimental ones. Based on the recorded data, the DFT results and a normal coordinate analysis based on a scaled quantum mechanical (SQM) force field approach, a complete vibrational assignment was made for the first time.
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Dimetoato/química , Inseticidas/química , Compostos Organotiofosforados/química , Modelos Moleculares , Teoria Quântica , Espectrofotometria Infravermelho , Análise Espectral RamanRESUMO
By contrast with the negative halochromic behaviour shown by phenolate betaines in the presence of alkaline and alkaline-earth cations, the addition of tetraalkylammonium salts to hydroxylic solutions of these dyes generate bathochromic shifts of their charge-transfer band. This positive halochromic behaviour by organic cations was examined systematically and its origin rationalized by nonspecific changes of the medium permittivity, and by specific dye-cation interactions in solution.
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Betaína/química , Corantes/química , Hidroxibenzoatos/química , Compostos de Amônio Quaternário/química , Cátions/química , Radical Hidroxila/química , Modelos Moleculares , Sais/químicaRESUMO
This paper reports a DFT modelling of SERS spectra for benzene and benzonitrile on the basis of a simple noncoordinate substrate-adsorbate model. Assignment of normal modes was obtained from internal force constants and potential energy distribution matrices and used to identify, according the SERS selection rules, the orientation of the optimized molecules on the metallic surface. Calculated band enhancements are in good agreement with experimental observations. The optimized geometry parameters of the molecule-Ag system, changes of HOMO-LUMO energies are discussed to give insight in the different SERS mechanisms for both molecules.
Assuntos
Derivados de Benzeno/química , Benzeno/química , Modelos Químicos , Nitrilas/química , Compostos Organometálicos/química , Teoria Quântica , Prata/química , Análise Espectral Raman/métodos , Propriedades de Superfície , TermodinâmicaRESUMO
The SERS modelling of o-, m-, and p-methoxybenzonitrile has been performed following the same methodology that in Part I. Optimized structure obtained from DFT calculations in a B3LYP-LANL2DZ level of calculation shows different tilted positions for the isomers under study. From correlations obtained by comparison of Raman and SERS spectra concerning geometrical parameters, frequency shifting, change in band intensity, and force constants is possible to give insight about the different effect of the metal surface on these molecules and the structural reasons of this behaviour. Frontier orbital analysis gives further information and reveals a ligand to metal charge transfer mechanism for all isomers, as well as its relative importance.