Designed long lived emission from CdSe quantum dots by reversible electronic energy transfer with a surface bound chromophore

The size-tunable emission of luminescent quantum dots (QDs) makes them highly interesting for applications that range from bioimaging to optoelectronics. For the same applications, engineering their luminescence lifetime – in particular, making it longer – would be as important; however, no rational methodology to reach this goal is available to date. Here we describe a strategy to prolong the emission lifetime of QDs by electronic energy shuttling to the triplet excited state of a surface-bound molecular chromophore. To implement this idea we made CdSe QDs of different sizes, and we self-assembled them with a pyrene derivative. We observed that the conjugates exhibit delayed luminescence, with emission decays that are prolonged by more than 3 orders of magnitude compared to the parent CdSe QDs (lifetimes up to 330 s). The mechanism invokes unprecedented reversible quantum dot-to-organic chromophore electronic energy transfer

Comparative analysis of the PET and ICT sensor properties of 1,8-naphthalimides containing aza-15-crown-5 ether moiety

International audienceNovel 4-amino- and 4-(acetyl)amino-N-aryl-1,8-naphthalimides containing aza-15-crown-5 ether receptor unit in the N-aryl fragment and at C-4 of the naphthalimide residue were designed and prepared. Significant internal charge transfer from electron donating amino or amido group at C-4 of the naphthalene ring to the acceptor carboxyimide moiety as well as photoinduced electron transfer between N-aryl receptor and the naphthalimide fragment was revealed by the UV/Vis absorption spectroscopy and considerable fluorescence quenching. The addition of calcium perchlorate to an acetonitrile solution of naphthalimides with the receptor at imide nitrogen hindered the photoinduced electron transfer process and accordingly restored the quenched fluorescence of the free ligands. In the case of the compound in which the aza-15-crown-5 receptor is located at C-4, the coordination with Ca2+ reduced the internal charge transfer interaction in the chromophore and caused a significant blue-shift of the absorption and emission peak. The observed spectral effects were analyzed using PM6 semiempirical calculations. Formation of complexes was also confirmed by 1H NMR spectroscopy

Photolariats: synthesis, metal ion complexation and photochromism

International audiencePhotolariat development, as an extension to the family of synthetic photochromic crown ether receptors, or photocrowns, is reported. Incorporated additional chelating groups, namely two anisoles or thioanisoles, contribute in completing the metal ion coordination sphere with different affinities and selectivities for a range of ions. Single-crystal X-ray diffraction analysis suggests that the thermally stable trans-form of the receptor is unsuitable for ion binding, consistent with spectrophotometric and NMR titration results, which is largely improved in the cis-form as the basis for the photocontrolled ion coordination/ejection. In terms of the azobenzene-containing receptor photochemistry, a photostationary state highly enriched in the cis-form (94:6, cis-/trans-) is reached, with slow thermal return (1.1-1.4 × 10− 5 s− 1) in the dark, which can undergo multiple cycles without discernable photodegradation

Metal-ion induced FRET in macrocyclic dynamic tweezers

International audienceAbstract We report here about effective FRET process (73-99%) in mono-Mg2+ complexes of symmetrical crown ether bis(styryl) dyes. The FRET process has not been observed in the free state and in binuclear complexes. The formation of mononuclear complex provides two styrylic fragments with appropriate positions of absorption and emission bands for FRET. The other important parameter for FRET is the proper geometric orientation of both chromophores, which attain sandwich conformation with close positioning of complexed and free styryl fragments induced by ion-modulated geometry reorganization of the bis-dye

Dynamics of ion-regulated photoinduced electron transfer in BODIPY-BAPTA conjugates

International audienceEfficient Ca2+-switched fluorescent sensors, where fluorescence output is governed by a light-activated ion-gated electron transfer pathway, can be obtained on combining BODIPY chromophores with a readily oxidized biocompatible and selective BAPTA receptor. Herein we report the synthesis and studies of two such conjugates, which vary in the nature of the spacer separating the two electroactive components, namely none (1) or phenyl (2). Single crystal X-ray crystallography and molecular modelling structures and calculations give information on molecular and electronic structure, while steady-state fluorescence experiments show high Ca2+-induced fluorescence enhancement factors of 122 and 23 and Kd values of 0.50 μM and 0.13 μM for 1 and 2, respectively. Notably, studies of the ultrafast photoinduced processes (through transient absorption spectroscopy) give access to electron transfer dynamics in pseudophysiological media as well as in a polar non-protic solvent and information about the fate of the excited molecules in the presence and absence of calcium. In water, electron transfer rates as high as 3.3 × 1012 s−1 and 8.3 × 1011 s−1 are measured for the ion-free, directly connected conjugate and the variant incorporating a phenyl spacer, respectively. This electron transfer pathway is efficiently blocked by the presence of an ion, restoring fluorescence

Org. Chem. Front.

The synthesis and characterization of an original π-extended cationic azahelicene is reported. The phenanthrene-fused aza[7]helicene derivative encompasses a total of ten aromatic fused rings leading to a dissymmetric yet helically folded structure, as revealed by NMR and X-ray diffraction analyses. The polyaromatic and cationic nature of the new azahelicenium makes it soluble in both organic and aqueous media, which allowed photophysical studies in solvents of different polarities. The extended chromophoric species demonstrates a broad absorption over the whole visible range and orange-red fluorescence emission. Chiral resolution of the racemate was performed subsequently, affording two optically pure and configurationally stable azahelicenium enantiomers. Multi-band circular dichroism and long-wavelength circularly polarized emission were observed, associated with remarkable absorption and luminescence dissymmetry factors, both in organic and aqueous media.Program Initiative d’Excellenc

Teaching Story without Struggle: Using Graded Readers and Their Audio Packs in the EFL Classroom

In recent years the support for extensive reading (ER) in English as a second or foreign language (ESL/EFL) programs has been compelling. When practicing extensive reading, the learner reads a wide variety of texts for pleasure and achieves a general understanding of the content while deciphering unknown words through context. This approach contrasts with intensive reading, a more traditional approach based on a slow, careful reading of a text, with goals of complete comprehension and the identification of specific details and information

Sub-Picosecond Time-Resolved Spectroscopy of Energetic Materials : the Nitromethane and Nitro-Stilbenes

Using sub-picosecond CARS experiment we observed direct photolysis of liquid nitromethane after pulse excitation at 299 nm. We measured the dynamic behaviour under excitation of three main ground state Raman lines at 917 cm-l, 1400 cm-l and 2968 cm-1. We deduced an excited state lifetime of 1.1 +/- 0.3 ps and we measured a photolysis quantum yield at 299 nm of 24% +/- 5%. Using "pump-probe" experiments we observed the evolution of excited states of eight nitro-stilbene derivatives including 2,4,6,2',4',6'-hexanitro-stilbene (HNS). In the studied compounds important non-radiative desexcitation channels have been observed and their possible role on explosive process is discussed