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21.
Pérez-Ojeda ME Trastoy B López-Arbeloa Í Bañuelos J Costela Á García-Moreno I Chiara JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(47):13258-13268
New hybrid organic–inorganic dyes based on an azide‐functionalized cubic octasilsesquioxane (POSS) as the inorganic part and a 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BDP) chromophore as the organic component have been synthesized by copper(I)‐catalyzed 1,3‐dipolar cycloaddition of azides to alkynes. We have studied the effects of the linkage group of BDP to the POSS unit and the degree of functionalization of this inorganic core on the ensuing optical properties by comparison with model dyes. The high fluorescence of the BDP dye is preserved in spite of the linked chain at its meso position, even after attaching one BDP moiety to the POSS core. The laser action of the new dyes has been analyzed under transversal pumping at 532 nm in both the liquid phase and when incorporated into solid polymeric matrices. The monosubstituted new hybrid dye exhibits high lasing efficiency of up to 56 % with high photostability, with its laser output remaining at the initial value after 4×105 pump pulses in the same position of the sample at a repetition rate of 30 Hz. However, functionalization of the POSS core with eight fluorophores leads to dye aggregation, as quantum mechanical simulation has revealed, worsening the optical properties and extinguishing the laser action. The new hybrid systems based on dye‐linked POSS nanoparticles open up the possibility of using these new photonic materials as alternative sources for optoelectronic devices, competing with dendronized or grafted polymers. 相似文献
22.
Kinetico‐Mechanistic Insights on the Assembling Dynamics of Allyl‐Cornered Metallacycles: The PtNpy Bond is the Keystone 下载免费PDF全文
Dr. Inmaculada Angurell Dr. Montserrat Ferrer Dr. Albert Gutiérrez Prof. Manuel Martínez Dr. Mercè Rocamora Dr. Laura Rodríguez Prof. Oriol Rossell Dipl.‐Chem. Yvonne Lorenz Dr. Marianne Engeser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(44):14473-14487
The square‐like homo‐ and heterometallamacrocycles [{Pd(η3‐2‐Me‐C3H4)( L n )2}2{M(dppp)}2](CF3SO3)6 (dppp=1,3‐bis(diphenylphosphino)propane) and [{Pd(η3‐2‐Me‐C3H4)( L1 )2}2{M(PPh3)2}2](CF3SO3)6 [py=pyridine, M=Pd, Pt, L n =4‐PPh2py ( L1 ), 4‐C6F4PPh2py ( L2 )] containing allyl corners were synthesised by antisymbiotic self‐assembly of the different palladium and platinum metallic corners and the ambidentate N,P ligands. All the synthesised assemblies displayed a complex dynamic behaviour in solution, the rate of which is found to be dependent on the electronic and/or steric nature of the different building blocks. A kinetico‐mechanistic study by NMR line shape analysis of the dynamics of some of these assemblies was undertaken in order to determine the corresponding thermal activation parameters. Both an enhanced thermodynamic stability and slower dynamics were observed for platinum‐pyridine‐containing species when compared with their palladium analogues. Time‐dependent NMR spectroscopy in combination with ESI mass spectrometry was used to study the exchange between the assemblies and their building blocks, as well as that occurring between different metallamacrocycles. Preliminary studies were carried out on the activity of some of the metallamacrocyclic compounds as catalytic precursors in the allylic substitution reaction, and the results compared with that of the monometallic allylic corner [Pd(η3‐2‐Me‐C3H4)( L1 )2]+. 相似文献
23.
Inmaculada Fernandez Robert Greatrex Norman N. Greenwood 《Journal of solid state chemistry》1980,34(1):121-128
99Ru Mössbauer spectra have been recorded at 4.2 K for the quaternary oxides Ba3Ru2MO9 (M = Mg, Ca, Sr; Co, Ni, Cu, Zn; and Cd), all of which crystallize with the hexagonal barium titanate structure. The Ca, Sr, and Cd compounds give sharp symmetrical singlets with chemical isomer shifts typical of ruthenium in the +5 oxidation state. The absence of magnetic hyperfine splitting is consistent with the published interpretation of magnetic susceptibility data in terms of binuclear intracluster spin pairing which leads to an S = 0 ground state. In contrast, magnetic hyperfine splitting is seen for the Mg, Zn, Co, Ni, and Cu compounds; this can be interpreted only in terms of long-range magnetic order and the absence of such an S = 0 ground state at 4.2 K. This differs from the published interpretation of the magnetic susceptibility data for Ba3Ru2MgO9 in the low-temperature region. The magnetic flux densities at the ruthenium nuclei in the magnetically ordered compounds (32.5–51.6 T) are lower than those normally associated with ruthenium(V), and the spectra cannot be curve fitted satisfactorily with single hyperfine patterns having the natural linewidth. Possible reasons for these observations are discussed. 相似文献
24.
Elena Fernández Manuel Ortuño Andrés Márquez Rosa Fuentes Inmaculada Pascual 《Optik》2010,121(2):151-158
Holographic data pages were stored in a polyvinyl alcohol (PVA)/acrylamide (AA) photopolymer. This material is formed of AA photopolymers which are considered interesting materials for recording holographic memories. A liquid crystal device was used to modify the object beam and store the data pages in the material. During the storage process, some parameters like exposure time, beam ratio and reading beam intensity were controlled to obtain high image quality after the reconstruction process. The bit error rate (BER) was calculated fitting the histograms of the images to determine what parameters improve the quality of the images. 相似文献
25.
Andrés-Tomé I Fyson J Dias FB Monkman AP Iacobellis G Coppo P 《Dalton transactions (Cambridge, England : 2003)》2012,41(28):8669-8674
Phosphorescent copper(I) complexes carrying 2,2'-bipyridyl derivatives and phosphine ligands have been prepared and fully characterised. The role of the bipyridyl as well as the phosphine ligands in defining the optical, as well as the chemical properties of the complexes, are discussed. The light emission of these complexes is investigated as a function of the molecular geometry: rigid complexes with restricted freedom to rearrange in the excited state are found to show a quantum yield of phosphorescence one order of magnitude higher than those complexes with no steric constraint. The complexes have been extruded in a polymer matrix as a proof of principle of their processability. 相似文献
26.
M. Eugenia Pérez‐Ojeda Dr. Beatriz Trastoy Álvaro Rol Dr. María D. Chiara Prof. Dr. Inmaculada García‐Moreno Dr. Jose Luis Chiara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6630-6640
A general procedure for the assembly of hetero‐bifunctional cubic silsesquioxanes with diverse functionality and a perfectly controlled distribution of functional groups on the inorganic framework has been developed. The method is based on a two‐step sequence of mono‐ and hepta‐functionalization through the ligand‐accelerated copper(I)‐catalyzed azide–alkyne cycloaddition of a readily available octaazido cubic silsesquioxane. The stoichiometry of the reactants and the law of binomial distribution essentially determine the selectivity of the key monofunctionalization reaction when a copper catalyst with strong donor ligands is used. The methodology has been applied to the preparation of a set of bifunctional nano‐building‐blocks with orthogonal reactivity for the controlled assembly of precisely defined hybrid nanomaterials and a fluorescent multivalent probe for application in targeted cell‐imaging. The inorganic cage provides an improved photostability to the covalently attached dye as well as a convenient framework for the 3D multivalent display of the pendant epitopes. Thus, fluorescent bioprobes based on well‐defined cubic silsesquioxanes offer interesting advantages over more conventional fully organic analogues and ill‐defined hybrid nanoparticles and promise to become powerful tools for the study of cell biology and for biomedical applications. 相似文献
27.
Inmaculada García Cuesta José Sánchez-Marín Alfredo M J Sánchez de Merás 《Chemphyschem》2006,7(2):508-513
Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) complexes have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE2- has D2d symmetry in vacuum as well as in the solvents dichloromethane and acetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoretical results are compared to the experimental data and good agreement is achieved. 相似文献
28.
Accurate control of a liquid-crystal display to produce a homogenized Fourier transform for holographic memories 总被引:1,自引:0,他引:1
Márquez A Gallego S Méndez D Alvarez ML Fernández E Ortuño M Neipp C Beléndez A Pascual I 《Optics letters》2007,32(17):2511-2513
We show an accurate procedure to obtain a Fourier transform (FT) with no dc term using a commercial twisted-nematic liquid-crystal display. We focus on the application to holographic storage of binary data pages, where a drastic decrease of the dc term in the FT is highly desirable. Two different codification schemes are considered: binary pi radians phase modulation and hybrid ternary modulation. Any deviation in the values of the amplitude and phase shift generates the appearance of a strong dc term. Experimental results confirm that the calculated configurations provide a FT with no dc term, thus showing the effectiveness of the proposal. 相似文献
29.
Chromophore systems consisting of one (compound 5) or two (compound 6) phenothiazine rings covalently attached to a bis-piperazinexylene chain were synthesized and evaluated as DNA photocleaving agents. In the presence of DNA, the compounds were shown to monointercalate in their deaggregated forms and to strongly absorb red wavelengths of light. Reactions containing micromolar concentrations of compound produced robust photocleavage of plasmid DNA under near-physiological conditions of temperature and pH (22 °C and pH 7.0). Phenothiazines 5 and 6 increased the Tm of calf thymus DNA by 17 and 19 °C, indicating that significant levels of duplex stabilization were produced. 相似文献
30.