Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 45
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
J Phys Chem Lett ; 11(15): 6063-6067, 2020 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-32635727

RESUMO

Two-photon-excited fluorescence spectroscopy is a powerful tool to study the structural and electronic properties of optically active complexes and molecules. Although numerous lanthanide complexes have been characterized by two-photon-excited fluorescence in solution, this report is the first to apply such a technique to actinide compounds. Contrasting with previous observations in lanthanides, we demonstrate that the two-photon absorption properties of the complexes significantly depend on the metal (4f vs 5f), with Cm(III) complexes showing significantly higher two-photon absorption cross sections than lanthanide analogues and up to 200-fold stronger emission intensities. These results are consistent with electronic and structural differences between the lanthanide and actinide systems studied. Hence, the described methodology can provide valuable insights into the interactions between f-elements and ligands, along with promising prospects on the characterization of scarce compounds.

2.
Chemistry ; 26(17): 3818-3828, 2020 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-31943360

RESUMO

We describe the synthesis of a series of covalently linked dimers of quadrupolar curcuminoid-BF2 dyes and the detailed investigation of their solvent-dependent spectroscopic and photophysical properties. In solvents of low polarity, intramolecular folding induces the formation of aggregated chromophores, the UV/Vis absorption spectra of which display the optical signature characteristic of weakly-coupled H-aggregates. The extent of folding and, in turn, of ground-state aggregation is strongly dependent on the nature of the flexible linker. Steady-state and time-resolved fluorescence emission spectroscopies show that the Frenkel exciton relaxes into a fluorescent symmetrical excimer state with a long lifetime. Furthermore, our in-depth studies show that a weakly emitting excimer lies on the pathway toward a photocyclomer. Two-dimensional 1 H NMR spectroscopy and density functional theory (DFT) allowed the structure of the photoproduct to be established. To our knowledge, this represents the first example of a [2π+2π] photodimerization of the curcuminoid chromophore.


Assuntos
Diarileptanoides/química , Solventes/química , Fluorescência , Espectroscopia de Ressonância Magnética , Teoria Quântica , Espectrometria de Fluorescência
3.
Chem Asian J ; 14(11): 1921-1925, 2019 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-30912261

RESUMO

Thermally activated delayed fluorescence (TADF) based on through-space donor and acceptor interactions constitute a recent and promising approach to develop efficient TADF emitters. Novel TADF isomers using a dithia[3.3]-paracyclophane building block as a versatile 3D platform to promote through-space interactions are presented. Such a 3D platform allows to bring together the D and A units into close proximity and to probe the effect of their orientation, contact site and distance on their TADF emission properties. This study provides evidence that the dithia[3.3]paracyclophane core is a promising platform to control intramolecular through-space interactions and obtain an efficient TADF emission with short reverse-intersystem crossing (RISC) lifetimes. In addition, this study demonstrates that this design can tune the energy levels of the triplet states and leads to an upconversion from 3 CT to 3 LE that promotes faster and more efficient RISC to the 1 CT singlet state.

4.
J Phys Chem A ; 123(1): 194-201, 2019 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-30565921

RESUMO

The conformational feature of noncovalent complexes of two borondifluoride chalcone derivatives was assessed using DFT-D2. The corresponding optical properties were analyzed based on time-dependent density functional theory calculations. As already described in such complexes, the π-stacking interaction existing between both fragments allowed formation of a new absorption band corresponding to the S0 → S1 transition. However, this band appears very close to the most intense band corresponding the S0 → S2 transition.

5.
Phys Chem Chem Phys ; 20(38): 24623-24632, 2018 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-30238104

RESUMO

In this work we present the synthesis, characterization and theoretical investigation of three boron-difluoride-curcuminoid derivatives and their covalent homodimers chemically linked through a polymethylenic chain. Low-lying electronic excited states and photophysical properties of the monomeric species have been described as the convolution of different donor-acceptor intramolecular excitations. Covalent dimers in solution can present open or folded structural conformations. Analysis of absorption profiles and computational results allow to identify the factors that control the relative stability of the two forms and rationalize its dependence with the solvent polarity. Interestingly, the strong electronic coupling in the folded forms results in low-lying excitations with sizable mixings of intra- and inter-chromophoric contributions, which cannot be described by means of the Kasha model of interacting chromophores. Our study demonstrates how decomposition of the computed excitations in terms of diabatic states can be extremely valuable in order to identify and quantify the nature of electronic transitions in the presence of several electron donor and acceptor fragments.

6.
Nano Lett ; 18(2): 1476-1482, 2018 02 14.
Artigo em Inglês | MEDLINE | ID: mdl-29369634

RESUMO

Metallic nanostructures permit controlling various photophysical processes by coupling photons with plasmonic oscillation of electrons confined in the tailored nanostructures. One example is hyperbolic metamaterial (HMM) leading to an enhanced spontaneous emission rate of emitters located nearby. Noting that emission in organic molecules is from either π-π* or intramolecular charge-transfer (ICT) states, we address here how HMM modifies ICT emission spectral features by comparing them with a spectral shift dependent on the local polarity of the medium. The 7.0 nm blue shift is observed in ICT emission from 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran dispersed into a polymer matrix prepared on HMM multilayered structure, while no spectral shift is observed in π-π* emission from perylene diimide. In the frame of the Lippert-Mataga formalism, the blue shift is explained by the HMM nonlocal effects resulting from 8% decrease in refractive index and 18% reduction in dielectric permittivity. This phenomenon was also shown in a hemicurcuminoid borondifluoride dye yielding 15.0 nm blue shift. Such a capability of spectral shift control in films by HMM structure opens new prospects for engineering organic light-emitting devices.

7.
Angew Chem Int Ed Engl ; 56(52): 16536-16540, 2017 12 22.
Artigo em Inglês | MEDLINE | ID: mdl-29105906

RESUMO

A family of organic emitters with a donor-σ-acceptor (D-σ-A) motif is presented. Owing to the weakly coupled D-σ-A intramolecular charge-transfer state, a transition from the localized excited triplet state (3 LE) and charge-transfer triplet state (3 CT) to the charge-transfer singlet state (1 CT) occurred with a small activation energy and high photoluminescence quantum efficiency. Two thermally activated delayed fluorescence (TADF) components were identified, one of which has a very short lifetime of 200-400 ns and the other a longer TADF lifetime of the order of microseconds. In particular, the two D-σ-A materials presented strong blue emission with TADF properties in toluene. These results will shed light on the molecular design of new TADF emitters with short delayed lifetimes.

8.
Inorg Chem ; 55(24): 12635-12643, 2016 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-27989201

RESUMO

In this work, we show that a dithienylethene (DTE) modified dipicolinic amide ligand can be a versatile tool to modulate Eu(III) and Yb(III) luminescence using light as an external stimulus. The nature of the modulation depends on the lanthanide emitter: with the europium ion, the DTE ligand quenches the red luminescence upon ring closure, whereas with the ytterbium ion, ring closure can be used to turn on the luminescence in the NIR range.

9.
Chemphyschem ; 17(14): 2128-36, 2016 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-26990918

RESUMO

Three boron diketonate chromophores with extended π-conjugated backbone were prepared and their spectroscopic features were investigated through a combined theoretical/experimental study. It was shown that these complexes, which undergo very large electronic reorganization upon photoexcitation, combine large two-photon absorption cross section with an emission energy and quantum efficiency in solution that is strongly dependent on solvent polarity. The strong positive influence of boron complexation on the magnitude of the two-photon absorption was clearly established, and it was shown that the two-photon absorption properties were dominated by the quadrupolar term. For one of the synthesized compounds, intense one- and two-photon-induced solid-state emission (fluorescence quantum yield of 0.65 with maximum wavelength of 610 nm) was obtained as a result of antiparallel J-aggregate crystal packing.

10.
Chemistry ; 22(15): 5219-32, 2016 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-26919627

RESUMO

The synthesis of boron difluoride complexes of a series of curcuminoid derivatives containing various donor end groups is described. Time-dependent (TD)-DFT calculations confirm the charge-transfer character of the second lowest-energy transition band and ascribe the lowest energy band to a "cyanine-like" transition. Photophysical studies reveal that tuning the donor strength of the end groups allows covering a broad spectral range, from the visible to the NIR region, of the UV-visible absorption and fluorescence spectra. Two-photon-excited fluorescence and Z-scan techniques prove that an increase in the donor strength or in the rigidity of the backbone results in a considerable increase in the two-photon cross section, reaching 5000 GM, with predominant two-photon absorption from the S0-S2 charge-transfer transition. Direct comparisons with the hemicurcuminoid derivatives show that the two-photon active band for the curcuminoid derivatives has the same intramolecular charge-transfer character and therefore arises from a dipolar structure. Overall, this structure-relationship study allows the optimization of the two-photon brightness (i.e., 400-900 GM) with one dye that emits in the NIR region of the spectrum. In addition, these dyes demonstrate high intracellular uptake efficiency in Cos7 cells with emission in the visible region, which is further improved by using porous silica nanoparticles as dye vehicles for the imaging of two mammalian carcinoma cells type based on NIR fluorescence emission.


Assuntos
Compostos de Boro/síntese química , Curcumina/química , Curcumina/síntese química , Corantes Fluorescentes/química , Ionóforos/química , Animais , Compostos de Boro/química , Fluorescência , Estrutura Molecular , Processos Fotoquímicos , Fótons , Teoria Quântica , Espectrometria de Fluorescência
11.
Phys Chem Chem Phys ; 18(7): 5299-305, 2016 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-26818786

RESUMO

1,4-Di-n-octyloxy-2,5-bis(pyren-1-ylethenyl)benzene (bis-pyrene) has been studied by the means of surface cavity ring-down (s-CRD) spectroscopy on an amorphous BK7 glass substrate and scanning tunnelling microscopy (STM) on Au(111). Absorption spectra show a modification of the optical properties as a function of coverage, i.e. appearance of a shoulder around 505 nm followed by a saturation of the intensity of this signal observed at higher coverages. We attribute this shoulder to the change of the molecular orientation between the first and the second monolayer and thus to an interfacial effect. These results are confirmed by scanning tunnelling microscopy (STM) measurements where the bis-pyrene molecules have been deposited on Au(111) at room temperature (RT) and onto a cold substrate. Independently of the temperature in the range from 210 K to RT, the first monolayer is always highly organized. At low temperature bis-pyrene molecules constituting the second monolayer are randomly distributed, suggesting that self-organisation is kinetically hindered. Deposited at room temperature, the molecular diffusion is enhanced and the formation of an organized second layer takes place after storing the sample for 150 minutes at room temperature. A HOMO-LUMO gap of 2.85 eV has been determined by scanning tunnelling spectroscopy, which is in very good agreement with the observed optical transition at 434 nm (2.86 eV) in s-CRD spectroscopy.

12.
Chemphyschem ; 17(1): 128-35, 2016 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-26538240

RESUMO

The photophysical and nonlinear optical properties of water-soluble chromophore-functionalised tris-dipicolinate complexes [LnL3](3-) (Ln=Yb and Nd) are thoroughly studied, revealing that only the Yb(III) luminescence can be sensitized by a two-photon excitation process. The stability of the complex in water is strongly enhanced by embedding in dispersible organosilicate nanoparticles (NPs). Finally, the spectroscopic properties of [NBu4]3 [YbL3] are studied in solution and in the solid state. The high brightness of the NPs allows imaging them as single objects using a modified two-photon microscopy setup in a NIR-to-NIR configuration.


Assuntos
Complexos de Coordenação/efeitos da radiação , Microscopia Confocal/métodos , Nanopartículas/efeitos da radiação , Ácidos Picolínicos/efeitos da radiação , Itérbio/química , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Luz , Nanopartículas/química , Ácidos Picolínicos/síntese química , Ácidos Picolínicos/química , Espectroscopia de Luz Próxima ao Infravermelho
13.
Org Biomol Chem ; 14(4): 1311-24, 2016 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-26660280

RESUMO

Hemicurcuminoids are based on half of the π-conjugated backbone of curcuminoids. The synthesis of a series of such systems and their borondifluoride complexes is described. The electrochemical and photophysical properties of difluorodioxaborine species were investigated as a function of the nature of electron donor and acceptor groups appended at either terminal positions of the molecular backbone. The emissive character of these dipolar dyes was attributed to an intraligand charge transfer process, leading to fluorescence emission that is strongly dependent on solvent polarity. Quasi-quantitative quenching of fluorescence in high polarity solvents was attributed to photoinduced electron transfer. These dyes were shown to behave as versatile fluorophores. Indeed, they display efficient two-photon excited fluorescence emission leading to high two-photon brightness values. Furthermore, they form nanoparticles in water whose fluorescence emission quantum yield is less than that of the dye in solution, owing to aggregation-induced fluorescence quenching. When cos7 living cells were exposed to these weakly-emitting nanoparticles, one- and two-photon excited fluorescence spectra showed a strong emission within the cytoplasm that originated from the individual molecules. Dye uptake thus involved a disaggregation mechanism at the cell membrane which restored fluorescence emission. This off-on fluorescence switching allows a selective optical monitoring of those molecules that do enter the cell, which offers improved sensitivity and selectivity of detection for bioimaging purposes.


Assuntos
Curcumina/análogos & derivados , Curcumina/análise , Corantes Fluorescentes/análise , Corantes Fluorescentes/síntese química , Hidrocarbonetos Halogenados/análise , Hidrocarbonetos Halogenados/química , Imagem Molecular/métodos , Animais , Células COS , Membrana Celular/química , Membrana Celular/metabolismo , Chlorocebus aethiops , Curcumina/química , Citoplasma/química , Fluorescência , Corantes Fluorescentes/química , Hidrocarbonetos Halogenados/síntese química , Estrutura Molecular , Nanopartículas/química , Fótons , Espectrometria de Fluorescência
14.
Inorg Chem ; 55(1): 114-24, 2016 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-26679038

RESUMO

A series of 10 tetradentate 1-hydroxy-pyridin-2-one (1,2-HOPO) ligands and corresponding eight-coordinated photoluminescent Eu(III) and Sm(III) complexes were prepared. Generally, the ligands differ by the linear (nLI) aliphatic linker length, from 2 to 8 methylene units between the bidentate 1,2-HOPO chelator units. The photoluminescent quantum yields (Φtot) were found to vary with the linker length, and the same trend was observed for the Eu(III) and Sm(III) complexes. The 2LI and 5LI bridged complexes are the brightest (Φtotxε). The change in ligand wrapping pattern between 2LI and 5LI complexes observed by X-ray diffraction (XRD) is further supported by density functional theory (DFT) calculations. The bimodal Φtot trends of the Eu(III) and Sm(III) complexes are rationalized by the change in ligand wrapping pattern as the bridge (nLI) is increased in length.


Assuntos
Európio/química , Samário/química , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Ligantes , Luminescência , Espectroscopia de Prótons por Ressonância Magnética , Soluções , Água/química
15.
Inorg Chem ; 54(14): 6807-20, 2015 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-26151082

RESUMO

The synthesis of a series of octadentate ligands containing the 1-hydroxypyridin-2-one (1,2-HOPO) group in complex with europium(III) is reported. Within this series, the central bridge connecting two diethylenetriamine units linked to two 1,2-HOPO chromophores at the extremities (5-LIN-1,2-HOPO) is varied from a short ethylene chain (H(2,2)-1,2-HOPO) to a long pentaethylene oxide chain (H(17O5,2)-1,2-HOPO). The thermodynamic stability of the europium complexes has been studied and reveals these complexes may be effective for biological measurements. Extension of the central bridge results in exclusion of the inner-sphere water molecule observed for [Eu(H(2,2)-1,2-HOPO)](-) going from a nonacoordinated to an octacoordinated Eu(III) ion. With the longer chain length ligands, the complexes display increased luminescence properties in aqueous medium with an optimum of 20% luminescence quantum yield for the [Eu(H(17O5,2)-1,2-HOPO)](-) complex. The luminescence properties for [Eu(H(14O4,2)-1,2-HOPO)](-) and [Eu(H(17O5,2)-1,2-HOPO)](-) are better than that of the model bis-tetradentate [Eu(5LIN(Me)-1,2-HOPO)2](-) complex, suggesting a different geometry around the metal center despite the geometric freedom allowed by the longer central chain in the H(mOn,2) scaffold. These differences are also evidenced by examining the luminescence spectra at room temperature and at 77 K and by calculating the luminescence kinetic parameters of the europium complexes.


Assuntos
Complexos de Coordenação/química , Európio/química , Substâncias Luminescentes/química , Piridonas/química , Complexos de Coordenação/síntese química , Ligantes , Substâncias Luminescentes/síntese química , Modelos Moleculares , Piridonas/síntese química , Termodinâmica
16.
J Phys Chem A ; 119(24): 6283-95, 2015 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-26020582

RESUMO

Controlling photoinduced intramolecular charge transfer at the molecular scale is key to the development of molecular devices for nanooptoelectronics. Here, we describe the design, synthesis, electronic characterization, and photophysical properties of two electron donor-acceptor molecular systems that consist of tolane and BF2-containing curcuminoid chromophoric subunits connected in a T-shaped arrangement. The two π-conjugated segments intersect at the electron acceptor dioxaborine core. From steady-state electronic absorption and fluorescence emission, we find that the photophysics of the dialkylamino-substituted analogue is governed by the occurrence of two closely lying excited states. From DFT calculations, we show that excitation in either of these two states results in a distinct shift of the electron density, whether it occurs along the curcuminoid or tolane moiety. Femtosecond transient absorption spectroscopy confirmed these findings. As a consequence, the nature of the emitting state and the photophysical properties are strongly dependent on solvent polarity. Moreover, these characteristics can also be switched by protonation or complexation at the nitrogen atom of the amino group. These features set new approaches toward the construction of a three-terminal molecular system in which the lateral branch would transduce a change of electronic state and ultimately control charge transport in a molecular-scale device.

17.
Chemistry ; 21(21): 7760-71, 2015 May 18.
Artigo em Inglês | MEDLINE | ID: mdl-25786789

RESUMO

The introduction of ester groups on the 5- and 15-meso positions of corroles stabilizes them against oxidation and induces a redshift of their absorption and emission spectra. These effects are studied through the photophysical and electrochemical characterization of up to 16 different 5,15-diester corroles, in which the third meso position is free or occupied by an aryl group, a long alkyl chain, or an ester moiety. Single-crystal X-ray structure analysis of five 5,15-diestercorroles and DFT and time-dependent DFT calculations show that the strong electron-withdrawing character of the 5,15 ester substituents is reinforced by their π overlap with the macrocyclic aromatic system. The crystal packing of corroles 2, 4, 6, 9, and 15 features short distances between chromophores that are stacked into columns thanks to the low steric hindrance of meso-ester groups. This close packing is partially due to intermolecular interactions that involve inner hydrogen and nitrogen atoms, and thereby, stabilize a single, identical corrole tautomeric form.

18.
Chem Commun (Camb) ; 50(96): 15140-3, 2014 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-25348258

RESUMO

Stepwise synthesis of linear nickel complex oligomer tapes with no need for solid-phase support has been achieved. The control of the length in flat arrays allows a fine-tuning of the absorption properties from the UV to the NIR region.


Assuntos
Complexos de Coordenação/química , Níquel/química , Complexos de Coordenação/síntese química , Cristalografia por Raios X , Conformação Molecular , Espectroscopia de Luz Próxima ao Infravermelho
19.
ACS Appl Mater Interfaces ; 6(1): 41-8, 2014 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-24341720

RESUMO

In this work, we investigate the effects of KrF nanosecond laser ablation on poly(methyl methacrylate) (PMMA) in combination with pyrene. Three materials containing PMMA were studied: (1) one doped with pure pyrene, (2) one doped with methyl 3-(1-pyrenyl)propanoate (so called alkylpyrene derivative thereafter), and (3) one grafted with pyrene. This last new material was developed by covalently bonding pyrene molecules to PMMA side-chains. A comparative study was undertaken to determine and compare the respective properties of the PMMA dye containing pyrene during nanosecond laser ablation at 248 nm. Cavities were etched for each material with up to 20 pulses for fluences between 0.03 and 1.7 J/cm(2) in samples containing 1, 2, and 4 mol % chromophore. The threshold fluences and the effective absorption coefficients were obtained. It was observed that effective absorption coefficients increased and threshold fluences decreased with the chromophore percentages in each kind of sample. Ablation parameters were not significantly modified when the dopant was changed from pyrene to the alkylpyrene derivative. On the other hand, when pyrene molecules were grafted on the polymer, the threshold fluences decreased, whereas the effective absorption coefficients became similar at fluences above 0.6 J/cm(2).

20.
Phys Chem Chem Phys ; 15(41): 18235-42, 2013 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-24064912

RESUMO

Incorporating in a non-covalent manner lanthanide derivatives into protein crystals has shown to be of prime interest for X-ray crystallography, insofar as these versatile compounds can co-crystallize with proteins through supramolecular interactions, in addition to being strong anomalous scatterers for anomalous-based diffraction techniques. In this paper, the selective affinity of tris-dipicolinate lanthanide complexes for cationic amino-acid residues is explored, using a panel of experimental (X-ray diffraction, NMR titration) and theoretical methods that provides access to an accurate description of the interaction process.


Assuntos
Complexos de Coordenação/química , Elementos da Série dos Lantanídeos/química , Ácidos Picolínicos/química , Proteínas/química , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Proteínas de Plantas/química , Proteínas de Plantas/metabolismo , Estrutura Terciária de Proteína , Proteínas/metabolismo , Urato Oxidase/química , Urato Oxidase/metabolismo
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA