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1.
A series of highly efficient deep red to near‐infrared (NIR) emissive organic crystals 1 – 3 based on the structurally simple 2′‐hydroxychalcone derivatives were synthesized through a simple one‐step condensation reaction. Crystal 1 displays the highest quantum yield (Φf) of 0.32 among the reported organic single crystals with an emission maximum (λem) over 710 nm. Comparison between the bright emissive crystals 1 – 3 and the nearly nonluminous compounds 4 – 7 clearly gives evidence that a subtle structure modification can arouse great property changes, which is instructive in designing new high‐efficiency organic luminescent materials. Notably, crystals 1 – 3 exhibit amplified spontaneous emissions (ASE) with extremely low thresholds. Thus, organic deep red to NIR emissive crystals with very high Φf have been obtained and are found to display the first example of NIR fluorescent crystal ASE.  相似文献   

2.
3‐(2,2′‐Bipyridyl)‐substituted iminocoumarin molecules (compounds 1 and 2 ) exhibit dual fluorescence. Each molecule has one electron donor and two electron acceptors that are in conjugation, which leads to fluorescence from two independent charge transfer (CT) states. To account for the dual fluorescence, we subscribe to a kinetic model in which both CT states form after rapid decays from the directly accessed S1 and S2 excited states. Due to the slow internal conversion from S2 to S1, or more likely the slow interconversion between the two subsequently formed CT states, dual emission is allowed to occur. This hypothesis is supported by the following evidence: 1) the emission at short and long ends of the spectrum originates from two different excitation spectra, which eliminates the possibility that dual emission occurs after an adiabatic reaction at the S1 level. 2) The fluorescence quantum yield of compound 2 grows with increasing excitation wavelength, which indicates that the high‐energy excitation elevates the molecule to a weakly emissive state that does not internally convert to the low‐energy, highly emissive state. The intensity of the two emission bands of 1 is tunable through the specific interactions between either of the two electron acceptors with another species, such as Zn2+ in the current demonstration. Therefore, the development of ratiometric fluorescent indicators based on the dual‐emitting iminocoumarin system is conceivable. Further fundamental studies on this series of compounds using time‐resolved spectroscopic techniques, and explorations of their applications will be carried out in the near future.  相似文献   

3.
An environment‐sensitive fluorophore can change its maximum emission wavelength (λem), fluorescence quantum yield (Φf), and fluorescence lifetime in response to the surrounding environment. We have developed two new intramolecular charge‐transfer‐type environment‐sensitive fluorophores, DBThD‐IA and DBSeD‐IA, in which the oxygen atom of a well‐established 2,1,3‐benzoxadiazole environment‐sensitive fluorophore, DBD‐IA, has been replaced by a sulfur and selenium atom, respectively. DBThD‐IA is highly fluorescent in n‐hexane (Φf=0.81, λem=537 nm) with excitation at 449 nm, but is almost nonfluorescent in water (Φf=0.037, λem=616 nm), similarly to DBD‐IA (Φf=0.91, λem=520 nm in n‐hexane; Φf=0.027, λem=616 nm in water). A similar variation in fluorescence properties was also observed for DBSeD‐IA (Φf=0.24, λem=591 nm in n‐hexane; Φf=0.0046, λem=672 nm in water). An intensive study of the solvent effects on the fluorescence properties of these fluorophores revealed that both the polarity of the environment and hydrogen bonding with solvent molecules accelerate the nonradiative relaxation of the excited fluorophores. Time‐resolved optoacoustic and phosphorescence measurements clarified that both intersystem crossing and internal conversion are involved in the nonradiative relaxation processes of DBThD‐IA and DBSeD‐IA. In addition, DBThD‐IA exhibits a 10‐fold higher photostability in aqueous solution than the original fluorophore DBD‐IA, which allowed us to create a new robust molecular nanogel thermometer for intracellular thermometry.  相似文献   

4.
《化学:亚洲杂志》2017,12(16):2104-2120
A series of charge‐neutral AuIII complexes, which comprise a dicarbanionic C‐deprotonated biphenyl ligand and bidentate ancillary ligands ([Au(C^C)(L^X)]; L^X=β‐diketonate and relatives (O^O), quinolinolate and relatives (N^O), and diphosphino (P^P) ligands), were prepared. All the complexes are emissive in degassed CH2Cl2 solutions and in thin‐film samples with Φ em up to 18 and 35 %, respectively, except for 5 and 6 , which bear (N^O)‐type ancillary ligands. Variation of the electronic characteristics of the β‐diketonate ancillary ligand was demonstrated to be a viable route for tuning the emission color from blue‐green (peak λ em at ca. 466 nm for 1 and 2 ; 501 nm for 4 a and 4 b ) to orange (peak λ em at 585 nm for 3 ), in contrast to the common observations that the ancillary ligand has a negligible effect on the excited‐state energy of the AuIII complexes reported in the literature. DFT/time‐dependent (TD) DFT calculations revealed that the energies of the 3ππ*(C^C) and the 3ILCT(O^O) excited states (ILCT=intraligand charge transfer) switch in order on going from O^O=acetylacetonate (acac) to aryl‐substituted β‐diketonate ligands. Solution‐processed and vacuum‐deposited organic light‐emitting diode (OLED) devices of selected complexes were prepared. The vacuum‐deposited OLED fabricated with 2 displays a sky‐blue emission with a maximum external quantum efficiency (EQE) of 6.71 % and CIE coordinates of (0.22, 0.40). The crystal structures of 7 and 9 reveal short intermolecular AuIII⋅⋅⋅AuIII contacts, with intermetal distances of 3.408 and 3.453 Å, respectively. DFT/TDDFT calculations were performed on 7 and 9 to account for the noncovalent interactions. Solid samples of 1 , 3 , and 9 exhibit excimeric emission at room temperature, which is rarely reported in AuIII complexes.  相似文献   

5.
Aminonaphthalimide–BODIPY energy transfer cassettes were found to show very fast (kEET≈1010–1011 s?1) and efficient BODIPY fluorescence sensitization. This was observed upon one‐ and two‐photon excitation, which extends the application range of the investigated bichromophoric dyads in terms of accessible excitation wavelengths. In comparison with the direct excitation of the BODIPY chromophore, the two‐photon absorption cross‐section δ of the dyads is significantly incremented by the presence of the aminonaphthalimide donor [δ≈10 GM for the BODIPY versus 19–26 GM in the dyad at λexc=840 nm; 1 GM (Goeppert–Mayer unit)=10?50 cm4 s molecule?1 photon?1]. The electronic decoupling of the donor and acceptor, which is a precondition for the energy transfer cassette concept, was demonstrated by time‐dependent density functional theory calculations. The applicability of the new probes in the one‐ and two‐photon excitation mode was demonstrated in a proof‐of‐principle approach in the fluorescence imaging of HeLa cells. To the best of our knowledge, this is the first demonstration of the merging of multiphoton excitation with the energy transfer cassette concept for a BODIPY‐containing dyad.  相似文献   

6.
The design of new molecules for photochemical studies typically requires knowledge of spectral features of pertinent chromophores beginning with the absorption spectrum (λ abs) and accompanying molar absorption coefficient (ε , m −1 cm−1) and often extending to the fluorescence spectrum (λ em) and fluorescence quantum yield (Φf), where the fluorescence properties may be of direct relevance or useful as proxies to gain insight into the nature of the first excited singlet state. PhotochemCAD databases, developed over a period of 30 years, are described here. The previous databases for 150 compounds have been expanded to encompass 339 compounds for which absorption spectra (including ε values), fluorescence spectra (including Φf values) and references to the primary literature have been included where available (552 spectra altogether). The compounds exhibit spectra in the ultraviolet, visible and/or near‐infrared spectral regions. The compound classes and number of members include acridines (21), aromatic hydrocarbons (41), arylmethane dyes (11), azo dyes (18), biomolecules (18), chlorins/bacteriochlorins (16), coumarins (14), cyanine dyes (19), dipyrrins (7), heterocycles (26), miscellaneous dyes (13), oligophenylenes (13), oligopyrroles (6), perylenes (5), phthalocyanines (11), polycyclic aromatic hydrocarbons (16), polyenes/polyynes (10), porphyrins (34), quinones (24) and xanthenes (15). A database of 31 solar spectra also is included.  相似文献   

7.
《化学:亚洲杂志》2017,12(24):3187-3194
A dual‐mechanism intramolecular charge transfer (ICT)–FRET fluorescent probe for the selective detection of H2O2 in living cells has been designed and synthesized. This probe used a coumarin–naphthalimide hybrid as the FRET platform and a boronate moiety as the recognition group. Upon the addition of H2O2, the probe exhibited a redshifted (73 nm) fluorescence emission, and the ratio of fluorescence intensities at λ =558 and 485 nm (F 558/F 485) shifted notably (up to 100‐fold). Moreover, there was a good linearity (R 2=0.9911) between the ratio and concentration of H2O2 in the range of 0 to 60 μm , with a limit of detection of 0.28 μm (signal to noise ratio (S/N)=3). This probe could also detect enzymatically generated H2O2. Importantly, it could be used to visualize endogenous H2O2 produced by stimulation from epidermal growth factor.  相似文献   

8.
Several donor-π-donor (D-π-D), acceptor-π-acceptor (A-π-A), and donor-π-acceptor (D-π-A) types of organic compounds with fluorene as π bridge and dimesitylboryl group as electron acceptor, which show strong two-photon excited blue fluorescence, have been synthesized and structurally investigated. The symmetric A-π-A type of compound exhibits the shortest wavelength of two-photon excited fluorescence (TPEF) at λem=405 nm under the excitation of λex=730 nm; the unsymmetric D-π-A type of compound with diphenylamino as donor exhibits the most intense TPEF at blue region (λem=484 nm) with a two-photon absorption cross-section of 425 GM under λex=800 nm.  相似文献   

9.
A high contrast tri‐state fluorescent switch (FSPTPE) with both emission color change and on/off switching is achieved in a single molecular system by fusing the aggregation‐induced emissive tetraphenylethene (TPE) with a molecular switch of spiropyran (SP). In contrast to most of the reported solid‐state fluorescent switches, FSPTPE only exists in the amorphous phase in the ring‐closed form owing to its highly asymmetric molecular geometry and weak intermolecular interactions, which leads to its grinding‐inert stable cyan emission in the solid state. Such an amorphous phase facilitates the fast response of FSPTPE to acidic gases and induces the structural transition from the ring‐closed form to ring‐open form, accompanied with the “Off” state of the fluorescence. The structural transition leads to a planar molecular conformation and high dipole moment, which further results in strong intermolecular interactions and good crystallinity, so when the acid is added together with a solvent, both the ring‐opening reaction and re‐crystallization can be triggered to result in an orange emissive state. The reversible control between any two of the three states (cyan/orange/dark) can be achieved with acid/base or mechanical force/solvent treatment. Because of the stable initial state and high color contrast (Δλ=120 nm for cyan/orange switch, dark state ΦF<0.01 %), the fluorescent switch is very promising for applications such as displays, chemical or mechanical sensing, and anti‐counterfeiting.  相似文献   

10.
The synthesis, one‐ and two‐photon absorption (TPA) and emission properties of two novel 2,6‐anthracenevinylene‐based copolymers, poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐carbazolevinyl‐ene] ( P1 ) and poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinyl‐ene‐alt‐N‐octyl‐2,7‐carbazolevinylene] ( P2 ) were reported. The as‐synthesized polymers have the number‐average molecular weights of 1.56 × 104 for P1 and 1.85 × 104 g mol?1 for P2 and are readily soluble in common organic solvents. They emit strong bluish‐green one‐ and two‐photon excitation fluorescence in dilute toluene solution (? P1 = 0.85, ? P2 = 0.78, λem( P1 ) = 491 nm, λem( P2 ) = 483 nm). The maximal TPA cross‐sections of P1 and P2 measured by the two‐photon‐induced fluorescence method using femtosecond laser pulses in toluene are 840 and 490 GM per repeating unit, respectively, which are obviously larger than that (210 GM) of poly[9,10‐bis‐(3,4‐bis(2‐ethylhexyloxy) phenyl)‐2,6‐anthracenevinylene], indicating that the poly(2,6‐anthracenevinylene) derivatives with large TPA cross‐sections can be obtained by inserting electron‐donating moieties into the polymer backbone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 463–470, 2010  相似文献   

11.
We demonstrate a reversible shape‐morphing with concurrent fluorescence switching in the nanomaterials which are complexed with cucurbit[7]uril (CB[7]) in water. The cyanostilbene derivative alone forms ribbon‐like two‐dimensional (2D) nanocrystals with bright yellow excimeric emission in water (λem=540 nm, ΦF=42 %). Upon CB[7] addition, however, the ribbon‐like 2D nanocrystals immediately transform to spherical nanoparticles with significant fluorescence quenching and blue‐shifting (λem=490 nm, ΦF=1 %) through the supramolecular complexation of the cyanostilbene and CB[7]. Based on this reversible fluorescence switching and shape morphing, we could demonstrate a novel strategy of turn‐on fluorescence sensing of spermine and also monitoring of lysine decarboxylase activity.  相似文献   

12.
Hydrogen sulfide (H2S) is connected with various physiological and pathological functions. However, understanding the important functions of H2S remains challenging, in part because of the lack of tools for detecting endogenous H2S. Herein, compounds Ratio‐H2S 1/2 are the first FRET‐based mitochondrial‐targetable dual‐excitation ratiometric fluorescent probes for H2S on the basis of H2S‐promoted thiolysis of dinitrophenyl ether. With the enhancement of H2S concentration, the excitation peak at λ≈402 nm of the phenolate form of the hydroxycoumarin unit drastically increases, whereas the excitation band centered at λ≈570 nm from rhodamine stays constant and can serve as a reference signal. Thus, the ratios of fluorescence intensities at λ=402 and 570 nm (I402/I570) exhibit a drastic change from 0.048 in the absence of H2S to 0.36 in the presence of 180 μM H2S; this is a 7.5‐fold variation in the excitation ratios. The favorable properties of the probe include the donor and acceptor excitation bands, which exhibit large excitation separations (up to 168 nm separation) and comparable excitation intensities, high sensitivity and selectivity, and function well at physiological pH. In addition, it is demonstrated that the probe can localize in the mitochondria and determine H2S in living cells. It is expected that this strategy will lead to the development of a wide range of mitochondria‐targetable dual‐excitation ratiometric probes for other analytes with outstanding spectral features, including large separations between the excitation wavelengths and comparable excitation intensities.  相似文献   

13.
Two polymorphs emitting near‐infrared ( 1 R form: α phase, λem=702 nm, Φf=0.41) and orange‐red fluorescence ( 1 O form: β phase, λem=618 nm, Φf=0.05) were synthesized by finely controlling the crystallization conditions of compound 1 , a structurally simple excited‐state intramolecular proton transfer (ESIPT)‐active molecule. Multicolor amplified spontaneous emissions (ASEs) were realized, for the first time, based on these polymorphs. Notably, the 1 O crystal underwent heating‐induced phase transformation from the β phase to the α form in a single‐crystal to single‐crystal (SCSC) manner accompanied with an unprecedented ASE changing. The ASE behavior of polymorphs 1 R , 1 O as well as the ASE changing during SCSC was investigated. The feasibility of multicolor lasing based on the present organic polymorphs was confirmed, which may provide a new development strategy for organic laser science and technology.  相似文献   

14.
9‐Fluorenylidenemalononitrile (FDCN) or 1, 1‐diphenyl‐2,2‐dicyanoethylene (DPCN) reacted with 10‐methyl‐9,10‐dihydroacridine (AcrH2) under irradiation (λ 320 nm) to give couping products. In order to gain further insight into the mechanism of the photo‐induced reaction, the photophysics of the reactions of FDCN or DPCN with AcrH2 have been investigated by using UV‐vis spectroscopy, fluorescence spectroscopy, excitation spectroscopy and time‐resolved fluorescence spectroscopy, respectively. The results show that FDCN or DPCN interacts with AcrH2 in the ground states to form a charge transfer complex, which further reacts to give the coupling product upon. irradiation.  相似文献   

15.
Highly efficient phosphor‐converted light‐emitting diodes (pc‐LEDs) are popular in lighting and high‐tech electronics applications. The main goals of present LED research are increasing light quality, preserving color point stability and reducing energy consumption. For those purposes excellent phosphors in all spectral regions are required. Here, we report on ultra‐narrow band blue emitting oxoberyllates AELi2[Be4O6]:Eu2+ (AE=Sr,Ba) exhibiting a rigid covalent network isotypic to the nitridoalumosilicate BaLi2[(Al2Si2)N6]:Eu2+. The oxoberyllates’ extremely small Stokes shift and unprecedented ultra‐narrow band blue emission with fwhm ≈25 nm (≈1200 cm?1) at λem=454–456 nm result from its rigid, highly condensed tetrahedra network. AELi2[Be4O6]:Eu2+ allows for using short‐wavelength blue LEDs (λem<440 nm) for efficient excitation of the ultra‐narrow band blue phosphor, for application in violet pumped white RGB phosphor LEDs with improved color point stability, excellent color rendering, and high energy efficiency.  相似文献   

16.
Despite the success of thermally activated delayed fluorescent (TADF) materials in steering the next generation of organic light‐emitting diodes (OLEDs), effective near infrared (NIR) TADF emitters are still very rare. Here, we present a simple and extremely high electron‐deficient compound, 5,6‐dicyano[2,1,3]benzothiadiazole (CNBz), as a strong electron‐accepting unit to develop a sufficiently strong donor‐acceptor (D?A) interaction for NIR emission. End‐capping with the electron‐donating triphenylamine (TPA) unit created an effective D?A?D type system, giving rise to an efficient NIR TADF emissive molecule (λem=750 nm) with a very small ΔEST of 0.06 eV. The electroluminescent device using this NIR TADF emitter exhibited an excellent performance with a high maximum radiance of 10020 mW Sr?1 m?2, a maximum EQE of 6.57% and a peak wavelength of 712 nm.  相似文献   

17.
A new hybrid photostable saponite clay with embedded donor–acceptor dyes was prepared and characterized in this work. The saponite is intercalated with a luminescent polyhedral oligomeric silsesquioxane, which transfers the photoexcitation energy directly to an acceptor dye (rhodamine B). The obtained composite material was characterized by means of XRD, TEM microscopy, and UV/Vis and photoluminescence spectroscopy. A physicochemical study showed that the system behaved as an efficient Förster resonance energy transfer pair, owing to the very good spectral overlap of donor emission (λem=510–540 nm) and acceptor absorption in the λ=530–570 nm range. The hybrid material represents the first example of a photonic antenna based on a synthetic saponite clay and can be considered a step forward in the search for new, efficient, and stable materials suitable for light‐harvesting applications.  相似文献   

18.
Fluorescent nucleoside analogs, commonly used to explore nucleic acid dynamics, recognition and damage, frequently respond to a single environmental parameter. Herein we address the development of chromophores that can simultaneously probe more than one environmental factor while having each associated with a unique spectroscopic signature. We demonstrate that an isomorphic emissive pyridine‐modified 2‐deoxy‐uridine 1 , containing multiple sensory elements, responds to changes in acidity, viscosity, and polarity. Protonation of the pyridine moiety (pKa 4.4) leads to enhanced emission (λem=388 nm) and red‐shifted absorption spectra (λabs=319 nm), suggesting the formation of an intramolecular hydrogen bond with the neighboring pyrimidine carbonyl. This “locked” conformation can also be mimicked by increasing solvent viscosity, resulting in a stark enhancement of emission quantum yield. Finally, increasing solvent polarity substantially impacts the chromophore’s Stokes shift [from 5.8×103 cm?1 at ET(30)=36.4 kcal mol?1 to 9.3 ×103 cm?1 at ET(30)=63.1 kcal mol?1]. The opposite effect is seen for the impact of solvent polarity of the protonated form. The characteristic photophysical signature induced by each parameter facilitates the exploration of these environmental factors both individually and simultaneously.  相似文献   

19.
Two compounds, 9,10‐bis[2‐(quinolyl)vinyl]anthracene (BQVA) and 9,10‐bis[2‐(naphthalen‐2‐yl)vinyl]anthracene (BNVA), have been synthesised and investigated. Both of them have aggregation‐induced enhanced emission (AIEE) properties. Heteroatom‐assisted BQVA shows solvatochromism, reversible chromism properties and self‐assembly effects. When increasing the solvent polarities, the green solution of BQVA turns to orange with a redshift of the fluorescence emission wavelengths from λ=527 to 565 nm. Notably, BQVA exhibits reversible chromism properties, including mechano‐ and thermochromism. The as‐prepared BQVA powders show green fluorescence (λem=525 nm) and the colour can turn into orange (λem=573 nm) after grinding. Interestingly, the orange colour can return at high temperature. Based on these reversible chromism properties, a simple and convenient erasable board has been designed. Different from BQVA, non‐heteroatom‐assisted BNVA has no clear chromic processes. The results obtained from XRD, differential scanning calorimetry, single‐crystal analysis and theoretical calculations indicate that the chromic processes depend on the heteroatoms in BQVA. Additionally, BQVA also exhibits excellent self‐assembly effects in different solvents. Homogeneous nanospheres are formed in mixtures of tetrahydrofuran and water, which are then doped into silica nanoparticles and treated with 3‐aminopropyltriethoxysilane to give amino‐functionalised nanoparticles (BQVA?AFNPs). The BQVA?AFNPs could be used to stain protein markers in polyacrylamide gel electrophoresis.  相似文献   

20.
Mouse anti-human CD71 monoclonal antibody (anti-CD71) was conjugated with red quantum dots (QDs; 5.3 nm, emission wavelength λ em = 614 nm) and used to label HeLa cells successfully. Then green QD-labeled goat anti-mouse immunoglobulin G (IgG; the size of the green QDs was 2.2 nm; λ em = 544 nm) was added to bind the red-QD-conjugated anti-CD71 on the cell surface by immunoreactions. Such interaction between anti-CD71 and IgG lasted 4 min and was observed from the fluorescence spectra: the fluorescence intensity of the “red” peak at 614 nm increased by 32%; meanwhile that of the “green” one at 544 nm decreased by 55%. The ratio of the fluorescence intensities (I 544 nm/I 614 nm) decreased from 0.5 to 0.2. The fluorescence spectra as well as cell imaging showed that fluorescence resonance energy transfer took place between these two kinds of QDs on the HeLa cells through interactions between the primary antibody and the secondary antibody.  相似文献   

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