Understanding excited‐state dynamics is critical for improving the photoluminescence (PL) efficiency of exciplexes. A series of exciplexes based on conventional hole‐transporting materials as donor and newly developed phenylpyridinato boron derivatives as acceptor were investigated. High PL efficiencies were achieved in only some combinations, and a large difference in performance among combinations provided insight into nonradiative processes in exciplex systems. Furthermore, the triplet local excited states (3LE) of each donor and acceptor were found play an important role in triplet exciplex harvesting. Significant contributions from triplets were clearly observed when the charge‐transfer excited states (1CT and 3CT) and 3LE were ideally aligned. We also demonstrated fine control of relative energy alignment via the concentration to improve the PL efficiency. 相似文献
The synthesis of a donor–acceptor silicon phthalocyanine (SiPc)‐azafullerene (C59N) dyad 1 and of the first acceptor–donor–acceptor C59N‐SiPc‐C59N dumbbell triad 2 was accomplished. The two C59N‐based materials were comprehensively characterized with the aid of NMR spectroscopy, MALDI‐MS as well as DFT calculations and their redox and photophysical properties were evaluated with CV and steady‐state and time‐resolved absorption and photoluminescence spectroscopy measurements. Notably, femtosecond transient absorption spectroscopy assays revealed that both dyad 1 and triad 2 undergo, after selective photoexcitation of the SiPc moiety, photoinduced electron transfer from the singlet excited state of the SiPc moiety to the azafullerene counterpart to produce the charge‐separated state, with lifetimes of 660 ps, in the case of dyad 1 , and 810 ps, in the case of triad 2 . The current results are expected to have significant implications en route to the design of advanced C59N‐based donor–acceptor systems targeting energy conversion applications. 相似文献
Summary: Two new polymers containing 2‐pyrazoline units in the main chain were synthesized for the first time by a Suzuki polycondensation between a 2‐pyrazoline monomer and aryl diboronic esters. The polymers showed high photoluminescence (PL) in both the solution and the solid state; quantum yields of PL in toluene were higher than 76%. Thermogravimetric analysis and cyclic voltammetry showed that the polymers had high thermal stability and good reversibility under electrochemical oxidation.
New polymers ( 2 and 3 ) with strong photoluminescence and good reversibility under electrochemical oxidation were synthesized here. 相似文献
The interactions between β‐cyclodextrin (β‐CD) and the mixtures of cationic‐anionic surfactants in aqueous solution were investigated by surface tension and 1H NMR measurements. It was shown that the critical micelle concentration (cmc) increased linearly with the increase of β‐CD concentration. Furthermore, β‐CD formed 1∶1 inclusion complex with both cationic and anionic surfactants in the mixed surfactant systems, and no significant selective inclusion was observed. The thermodynamic parameters of the inclusion process of β‐CD to mixed cationic‐anionic surfactants were calculated by a numerical method based on the surface tension measurements, and it was found that the inclusion process was both enthalpy and entropy favorable. 相似文献
The molecular configuration and crystal structure of solid polycrystalline N,N′′‐diacetylbiuret (DAB), a potential nitrogen‐rich fertilizer, have been analyzed by a combination of solid‐ and liquid‐state NMR spectroscopy, X‐ray diffraction, and DFT calculations. Initially a pure NMR study (“NMR crystallography”) was performed as available single crystals of DAB were not suitable for X‐ray diffraction. Solid‐state 13C NMR spectra revealed the unexpected existence of two polymorphic modifications (α‐ and β‐DAB) obtained from different chemical procedures. Several NMR techniques were applied for a thorough characterization of the molecular system, revealing chemical shift anisotropy (CSA) tensors of selected nuclei in the solid state, chemical shifts in the liquid state, and molecular dynamics in the solid state. Dynamic NMR spectroscopy of DAB in solution revealed exchange between two different configurations, which raised the question, is there a correlation between the two different configurations found in solution and the two polymorphic modifications found in the solid state? By using this knowledge, a new crystallization protocol was devised which led to the growth of single crystals suitable for X‐ray diffraction. The X‐ray data showed that the same symmetric configuration is present in both polymorphic modifications, but the packing patterns in the crystals are different. In both cases hydrogen bonds lead to the formation of planes of DAB molecules. Additional symmetry elements, a two‐fold screw in the case of α‐DAB and a c‐glide plane in the case of β‐DAB, lead to a more symmetric (α‐DAB) or asymmetric (β‐DAB) intermolecular hydrogen‐bonding pattern for each molecule. 相似文献
The excitonic relaxation dynamics of perovskite adsorbed on mesoporous thin films of Al2O3 and NiO upon excitation at 450 nm were investigated with femtosecond optical gating of photoluminescence (PL) via up‐conversion. The temporal profiles of emission observed in spectral region 670–810 nm were described satisfactorily with a composite consecutive kinetic model and three transient components representing one hot and two cold excitonic relaxations. All observed relaxation dynamics depend on the emission wavelength, showing a systematic time–amplitude correlation for all three components. When the NiO film was employed, we observed an extent of relaxation proceeding through the non‐emissive surface state larger than through the direct electronic relaxation channel, which quenches the PL intensity more effectively than on the Al2O3 film. We conclude that perovskite is an effective hole carrier in a p‐type electrode for NiO‐based perovskite solar cells showing great performance. 相似文献
It has been reported that chiral dual system is able to improve the enantioseparation of enantiomers in many cases. Currently, the dual systems involved in CE chiral separation are mostly dual CDs systems, and the polysaccharides‐based chiral dual system was reported in only one paper. To the best of our knowledge, the use of chondroitin sulfate C (CSC)‐based dual system for enantiomeric separation has not been reported previously. Herein, four CSC‐based chiral dual systems, namely CSC/glycogen, CSC/chondroitin sulfate A (CSA), CSC/hydroxypropyl‐β‐CD (HP‐β‐CD), as well as CSC/β‐CD (β‐CD), were evaluated for the first time for their enantioseparation capability by CE in this paper. During the course of the work, the influences of chiral selector concentration and buffer pH values on enantioseparation in dual systems were systematically investigated. Under the optimized conditions, the dual system consisting of CSC and glycogen exhibited better separations toward nefopam, duloxetine, sulconazole, atenolol, laudanosine, and cetirizine enantiomers compared to the single CSC or glycogen system. The combination of CSC and HP‐β‐CD improved the separation of amlodipine and chlorphenamine enantiomers. However, no synergistic effect was observed in the CSC/CSA and CSC/β‐CD systems. 相似文献
DBPP (2,5‐di‐(2‐biphenyl)‐1,4‐phenylene) units were embedded into a PPV (poly(p‐phenylenevinylene)) backbone, resulting in a dramatic improvement in the solid‐state photoluminescence quantum efficiency of the polymer. Oxadiazole units were introduced as PPV main‐chain substitutents, imparting the resulting polymer with bipolar charge‐transporting properties. A carefully‐designed conjugated polymer combining both DBPP and oxadiazole units showed both high PL efficiency and bipolar charge transport ability, making it a promising candidate for the fabrication of efficient single‐layer LED devices. 相似文献
The human lectin galectin‐1 (hGal‐1) translates sugar signals, that is, β‐galactosides, into effects on the level of cells, for example, growth regulation, and has become a model for studying binding of biopharmaceutically relevant derivatives. Bound‐state conformations of Galβ‐C‐(1→3)‐Glcβ‐OMe ( 1 ) and its βGal‐(1→3)‐βGlc‐OMe disaccharide parent compound were studied by using NMR spectroscopy (transferred (TR)‐NOESY data), assisted by docking experiments and molecular dynamics (MD) simulations. The molecular recognition process involves a conformational selection event. Although free C‐glycoside access four distinct conformers in solution, hGal‐1 recognizes shape of a local minimum of compound 1 , the syn‐Φ/syn‐Ψ conformer, not the structure at global minimum. MD simulations were run to explain, in structural terms, the observed geometry of the complex. 相似文献
Energy transfer has been employed in third‐generation solar cells for the conversion of light into electrical energy. Long‐range nonradiative energy transfer from semiconductor quantum dots (QDs) to fluorophores has been demonstrated by using CdS QDs and thiophene?BODIPY (boron dipyrromethene, abbreviated as TG2). TG2 shows a broad photoluminescence (PL) spectrum, which varies with concentration. At very low concentrations, monomeric units are present; then, upon increasing the concentration, these monomers form a mixed (J‐/H‐)aggregated state. Energy transfer between the CdS QDs and TG2 was confirmed by separately investigating the interactions between CdS and the monomer of TG2 and between CdS and the aggregated states of TG2. Size‐dependent PL quenching confirmed that nonradiative Förster resonance energy transfer (FRET) from photoexcited CdS QDs to the J‐aggregate state of TG2 was the major energy‐relaxation channel, which occurred on the timescale of hundreds of fs. These results have broad applications in the field of light harvesting based on the assembly of molecular aggregates. 相似文献
Semiconductor nanocrystals (NCs) possess high photoluminescence (PL) typically in the solution phase. In contrary, PL rapidly quenches in the solid state. Efficient solid state luminescence can be achieved by inducing a large Stokes shift. Here we report on a novel synthesis of compositionally controlled CuCdS NCs in air avoiding the usual complexity of using inert atmosphere. These NCs show long‐range color tunability over the entire visible range with a remarkable Stokes shift up to about 1.25 eV. Overcoating the NCs leads to a high solid‐state PL quantum yield (QY) of ca. 55 % measured by using an integrating sphere. Unique charge carrier recombination mechanisms have been recognized from the NCs, which are correlated to the internal NC structure probed by using extended X‐ray absorption fine structure (EXAFS) spectroscopy. EXAFS measurements show a Cu‐rich surface and Cd‐rich interior with 46 % CuI being randomly distributed within 84 % of the NC volume creating additional transition states for PL. Color‐tunable solid‐state luminescence remains stable in air enabling fabrication of light‐emitting diodes (LEDs). 相似文献
The noncovalent interactions between 4′, 6‐diamidino‐2‐phenylindole (DAPI) and sulfobutylether β‐cyclodextrin (SBE7β‐CD) are evaluated by using photochemical measurements and compared with that of native β‐CD. Contrasting recognition behavior and intriguing modulations in the photochemical behavior of DAPI were observed. In particular, a large enhancement in the fluorescence emission and excited‐state lifetime were seen upon binding to SBE7β‐CD, with the SBE7β‐CD inclusion complex being approximately 1000 times stronger than that of β‐CD. The ensuing fluorescence “turn on” was demonstrated to be responsive to chemical stimuli, such as metal ions and adamantylanmine (AD). Upon addition of Ca2+/AD, nearly quantitative dissociation of the complex was established to regenerate the free dye and result in fluorescence “turn off”. The SO3? groups are believed to be critical for the strong and selective binding of the chromophore and the stimuli‐responsive tuning. This is as an important design criterion for the optimization of host–guest properties through supramolecular association, which is relevant for drug‐delivery applications. 相似文献