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1.
    
A series of new metal‐free blue emission compounds, i.e., diprotonated terpyH2ClPF6 ( 1 ), tterpyH2ClPF6 ( 2 ), ClterpyH2ClPF6 ( 3 ), and BterpyH2(PF6)2 ( 4 ), were prepared and characterized by electrospray ionization mass spectrometry, UV–vis spectroscopy, and cyclic voltammetry (CV). Abbreviations used are terpy = 2,2′:6′,2″‐terpyridine, tterpy = 4′‐(4‐tolyl)‐2,2′:6′,2″‐terpyridine, Clterpy = 4′‐chloro‐2,2′:6′,2″‐terpyridine, and Bterpy = 4,4′,4″‐tert‐butyl‐2,2′:6′,2″‐terpyridine. The X‐ray crystal structures of the three new compounds 1, 2, and 4 were determined. Both protonated pyridine rings of the terpyridine derivatives are hydrogen bonded intermolecularly to the adjacent Cl− ion in compounds 1 , 2, and 3 . The π–π* absorption bands in the UV region for 1, 2, 3, and 4 in acetonitrile were red‐shifted relative to those of the corresponding neutral compounds. All the compounds exhibited stronger emissions (around 400 nm) than their neutral counterparts. All the CVs for the diprotonated species, terpyH, tterpyH, ClterpyH, and BterpyH, showed the first reduction waves around −0.6 V, which were more positive than those of the neutral ones. Density functional theory was applied to interpret the remarkable differences in the interaction of the Cl− ion. The attachment of two protons to the two terminal Bterpy nitrogens in 4 elicits remarkable characteristics. Both positive charges on the nitrogens are delocalized over the conjugated pyridine systems and the tertiary carbonium ions are stabilized to lead to stronger emission (Φ = 0.35) than the corresponding neutral Bterpy (Φ = 0.045). CCDC 732045–732047 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

2.
    
Electronic structures of binuclear ruthenium complexes [Ru2(terpy)2(tppz)]4+ ( 1A ) and [Ru2Cl2(L)2(tppz)]2+ {L = bpy ( 2A ), phen ( 3A ), and dpphen ( 4A )} were studied by density functional theory calculations. Abbreviations of the ligands (Ls) are bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, dpphen = 4,7‐diphenyl‐1,10‐phenanthroline, terpy = 2,2′:6′,2″‐terpyridine, and tppz = tetrakis(2‐pyridyl)pyrazine. Their mononuclear reference complexes [Ru(terpy)2]2+ ( 1B ) and [RuClL(terpy)]+ {L = bpy ( 2B ), phen ( 3B ), and dpphen ( 4B )} were also examined. Geometries of these mononuclear and binuclear Ru(II) complexes were fully optimized. Their geometric parameters are in good agreement with the experimental data. The binuclear complexes were characterized by electrospray ionization mass spectrometry, UV–Vis spectroscopy, and cyclic voltammograms. Hexafluorophosphate salts of binuclear ruthenium complexes of 3A and 4A were newly prepared. The crystal structure of binuclear complex 1A (PF6)4 was also determined. Orbital interactions were analyzed to characterize the metal‐to‐ligand charge‐transfer (MLCT) states in these complexes. The Cl− ligand works to raise the orbital energy of the metal lone pair, which leads to the low MLCT state. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

3.
    
A systematic study on the surface‐enhanced Raman scattering (SERS) for 3,6‐bi‐2‐pyridyl‐1,2,4,5‐tetrazine (bptz) adsorbed onto citrate‐modified gold nanoparticles (cit‐AuNps) was carried out based on electronic and vibrational spectroscopy and density functional methods. The citrate/bptz exchange was carefully controlled by the stepwise addition of bptz to the cit‐AuNps, inducing flocculation and leading to the rise of a characteristic plasmon coupling band in the visible region. Such stepwise procedure led to a uniform decrease of the citrate SERS signals and to the rise of characteristic peaks of bptz, consistent with surface binding via the N heterocyclic atoms. In contrast, single addition of a large amount of bptz promoted complete aggregation of the nanoparticles, leading to a strong enhancement of the SERS signals. In this case, from the distinct Raman profiles involved, the formation of a new SERS environment became apparent, conjugating the influence of the local hot spots and charge‐transfer (CT) effects. The most strongly enhanced vibrations belong to a1 and b2 representations, and were interpreted in terms of the electromagnetic and the CT mechanisms: the latter involving significant contribution of vibronic coupling in the system. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

4.
吴乐琦  张建兵 《发光学报》1998,19(3):251-253
研究了在铝酸盐蓝色荧光粉ＢａＭｇＡｌ１０Ｏ１７：Ｅｕ中用Ｃａ代替部分Ｂａ的效果，结果表明，约４～１２ｍｏｌ％的Ｂａ和Ｃａ取代后，抑制了５００ｎｍ以上的工波绿色发射，色坐标Ｙ值减小，而发射峰强度增高，从而改善了这种蓝色荧光粉的性能。  相似文献   

5.
    
A concentration‐dependent Raman study of dimethyl formamide (DMF) in Ag nanocolloidal solution was carried out in order to observe the effect of concentration on the surface enhancement mechanism. The Raman spectra in the region 900–2200 cm−1 comprising four prominent Raman modes were measured experimentally and analyzed at five different concentrations: 1, 3, 5, 7, 10 mM , and in neat DMF. In order to find the possible configurations of DMF + Ag complexes, density functional theory (DFT) calculations were carried out taking one, three and five Ag atom clusters. The Raman spectra of unconjugated DMF, DMF + Ag and DMF + 3Ag complexes were calculated theoretically to assign the vibrational modes under consideration more accurately and to understand the wavenumber shift and change in intensity observed in experimental measurements. Water present in the colloidal solution may also conjugate with DMF and its complexes with Ag. In order to see the influence of water on the wavenumber shift and intensity changes, we have also obtained the optimized structures and Raman modes of DMF + water and DMF + water + Ag complexes. Good agreement between the experimental and theoretical wavenumber shifts has been obtained by using B3LYP functional theory and CEP‐31G basis set for the DMF + Ag complex. The experimental results suggest that the SERS enhancement is concentration‐dependent. The concentration‐dependent linewidth shows the existence of the phenomena of motional narrowing and diffusion dynamics in the colloidal solution. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

6.
    
There remains an urgent demand for high‐quality blue luminogens that can simultaneously achieve high photoluminescence quantum yield (PLQY) in film and high exciton utilization efficiency (EUE) in the electroluminescence (EL) process. In this study, a referable molecular design strategy is developed for blue luminogens via constructing low‐lying locally excited (LE) state with an aggregation‐induced emission (AIE) characteristic and high‐lying charge‐transfer (CT) state for the effective triplet‐to‐singlet conversion channel. 2TriPE‐BPI‐MCN with the insertion of p‐cyano and o‐methyl groups is designed to compare with its matrix framework (2TriPE‐BPI). They have analogous properties of the lowest singlet (S1) states with blue emission and free of concentration quenching in film; however, 2TriPE‐BPI‐MCN exhibits unusual response for hydrostatic pressure owing to its S2 state CT characteristics. Therefore, 2TriPE‐BPI‐MCN can harness more electrogenerated excitons than 2TriPE‐BPI, resulting in a better EL performance in nondoped blue organic light‐emitting diodes (OLEDs) (CIEx,y = 0.153, 0.147) with high external quantum efficiency of 4.6% and negligible efficiency roll‐off. These findings could open a feasible avenue to develop high‐quality blue luminogens for high‐performance nondoped blue OLEDs.  相似文献   

7.
    
IR, Raman and surface‐enhanced Raman scattering (SERS) spectra of 5‐sulphosalicylic acid were recorded and analysed. The vibrational wavenumbers were computed by density functional theoretical (DFT) method using B3LYP/6–31G* basis. The bands due to the stretching modes CO, C S and SO2 are intense in the SERS spectrum. The C H stretching mode also appears in the SERS spectrum. The molecule is found to adsorb through both the carboxyl and sulphonyl groups. A possible tilted orientation of the molecule is suggested. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

8.
    
Ruddlesden–Popper halide perovskite (RPP) materials are of significant interest for light‐emitting devices since their emission wavelength can be controlled by tuning the number of layers n, resulting in improved spectral stability compared to mixed halide devices. However, RPP films typically contain phases with different n, and the low n phases tend to be unstable upon exposure to humidity, irradiation, and/or elevated temperature which hinders the achievement of pure blue emission from n = 2 films. In this work, two spacer cations are used to form an RPP film with mixed cation bilayer and high n = 2 phase purity, improved stability, and brighter light emission compared to a single spacer cation RPP. The stabilization of n = 2 phase is attributed to favorable formation energy, reduced strain, and reduced electron–phonon coupling compared to the RPP films with only one type of spacer cation. Using this approach, pure blue light‐emitting diodes (LEDs) with Commission Internationale de l'éclairage (CIE) coordinates of (0.156, 0.088) and excellent spectral stability are achieved.  相似文献   

9.
The reaction channels of di‐tert‐butylcarbene ( 2 ), its radical anion, ( 3 ) and its radical cation ( 4 ) were investigated theoretically by using DFT/B3LYP with 6‐31+G(d) basis set and 6‐311+G(2d,p) for single point energy calculations. Conversion of the neutral carbene 2 to the charged species 3 and 4 results in significant geometric changes. In cation 4 two different types of C (CH3)3 bonds are observed: one elongated sigma bond called “axial” with 1.61 Å and two normal sigma bonds with a bond length of 1.55 Å. Species 2 and 4 have an electron deficient carbon center; therefore, migration of CH3 and H is observed from adjacent tert‐butyl groups with low activation energies in the range of 6–9 kcal/mol like similar Wagner–Meerwein rearrangements in the neopentyl‐cation system. Neutral carbene 2 shows C H insertion to give a cyclopropane derivative with an activation energy of 6.1 kcal/mol in agreement with former calculations. Contrary to species 2 and 4 , the radical anion 3 has an electron rich carbon center which results in much higher calculated activation energies of 26.3 and 42.1 kcal/mol for H and CH3 migrations, respectively. NBO charge distribution indicates that the hydrogen migrates as a proton. The central issue of this work is the question: how can tetra‐tert‐butylethylene ( 1 ) be prepared from reaction of either species 2 , 3 , or 4 as precursors? The ion–ion reaction between 3 and 4 to give alkene 1 with a calculated reaction enthalpy of 203.5 kcal/mol is extremely exothermic. This high energy decomposes alkene 1 after its formation into two molecules of carbene 2 spontaneously. Ion–molecule reaction of radical anion 3 with the neutral carbene 2 is a much better choice: via a proper oriented charge–transfer complex the radical anion of tetra‐tert‐butylethylene (11) is formed. The electron affinity of 1 was calculated to be negligible. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

10.
    
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11.
    
Vjeran Gomzi 《Molecular physics》2013,111(11):1419-1425
Two 5-methyl-2-thiocytosine (5-MTC) radical species formed in 5-methylcytosine hemihydrate crystal lattice have been investigated by means of g-tensor and spin density distribution calculation using the B3LYP density functional. Theoretical values have been compared with experimental data for g-tensor eigenvectors. In model structures containing more molecules, significant difference of spin density localization on 5-MTC has been found for radical cation (radical I) in comparison to neutral radical of cationic origin (radical II). The structure of the radical centre as well as the mechanism of charge transfer and radical stabilization on 5-MTC in this system has been proposed.  相似文献   

12.
    
The rigid molecular assembly formed by the fusion of the donor type acridine and acceptor type indolo[3,2,1‐jk]carbazole, namely 16,16‐dimethyl‐11,16‐dihydrodibenzo[2,3:5,6]pyrrolizino[1,7‐ab]acridine (ACDID), is developed as a new chromophore to give narrow emission in the blue region. The functionalization of the chromophore with phenyl and triphenylamine gives two fluorescence emitters, ACDID‐Ph and ACDID‐TPA, respectively. The in‐depth study of the emitters has confirmed that the triphenylamine unit in the ACDID‐TPA emitter enhances the external quantum efficiency (EQE) along with device stability. The ACDID‐TPA emitter shows high EQE of 6.3% and small full width at half maximum of 39 nm by the rigidity of the chromophore. The ACDID‐derived blue emitter performs better than the conventional pyrene‐derived emitter in terms of device lifetime, demonstrating the potential of the donor‐ and acceptor‐fused ACDID as the chromophore of blue emitters.  相似文献   

13.
    
A new design strategy is introduced to address a persistent weakness with resonance thermally activated delayed fluorescence (R‐TADF) emitters to reduce aggregation‐caused quenching effects, which are identified as one of the key limiting factors. The emitter Mes3DiKTa shows an improved photoluminescence quantum yield of 80% compared to 75% for the reference DiKTa in 3.5 wt% 1,3‐bis(N‐carbazolyl)benzene. Importantly, emission from aggregates, even at high doping concentrations, is eliminated and aggregation‐caused quenching is strongly curtailed. For both molecules, triplets are almost quantitatively upconverted into singlets in electroluminescence, despite a significant (≈0.21 eV) singlet‐triplet energy gap (ΔEST), in line with correlated quantum‐chemical calculations, and a slow reverse intersystem crossing. It is speculated that the lattice stiffness responsible for the narrow fluorescence and phosphorescence emission spectra also protects the triplets against nonradiative decay. An improved maximum external quantum efficiencies (EQEmax) of 21.1% for Mes3DIKTa compared to the parent DiKTa (14.7%) and, importantly, reduced efficiency roll‐off compared to literature resonance TADF organic light‐emitting diodes (OLEDs), shows the promise of this design strategy for future design of R‐TADF emitters for OLED applications.  相似文献   

14.
    
Three new color‐tunable (deep‐blue to sky‐blue) and solution‐processable emitters—9′‐(2,12‐di‐tert‐butyl‐5,9‐dioxa‐13b‐boranaphtho[3,2,1‐de]anthracen‐7‐yl)‐9′H‐9,3′:6′,9″‐tercarbazole ( TB‐3Cz) , 9′‐(2,12‐di‐tert‐butyl‐5,9‐dioxa‐13b‐boranaphtho[3,2,1‐de]anthracen‐7‐yl)‐9,9″‐diphenyl‐9H,9′H,9″H‐3,3′:6′,3″‐tercarbazole ( TB‐P3Cz) , and 9‐(2,12‐di‐tert‐butyl‐5,9‐dioxa‐13b‐boranaphtho[3,2,1‐de]anthracen‐7‐yl)‐N3,N3,N6,N6‐tetraphenyl‐9H‐carbazole‐3,6‐diamine ( TB‐DACz) —are demonstrated, which are cleverly designed and synthesized by appending a boron‐fused entity as an electron acceptor to different electron‐rich entities containing carbazole derivatives as donors. The thermal, photophysical, electrochemical, and electroluminescent characteristics of all the new materials are extensively investigated. Comprehensive photophysical investigations reveal that these emitters exhibit not only thermally activated delayed fluorescence (TADF) but also aggregation‐induced emission (AIE) properties. Consequently, solution‐processable organic light‐emitting diodes (OLEDs) fabricated using these new materials as nondoped emitters in the emissive layer exhibit a maximum external quantum efficiency (EQE) and Commission Internationale de l'Éclairage (CIE) color coordinates of 9.90% and (0.17, 0.07), respectively, for TB‐3Cz ; 6.13% and (0.15, 0.08), respectively, for TB‐P3Cz ; and 6.04% and (0.18, 0.40), respectively, for TB‐DACz . As far as it is known, the performance and ultrahigh color purity satisfying the deep‐blue CIE coordinates of the National Television System Committee (NTSC) for TB‐3Cz and TB‐P3Cz are the highest reported thus far for nondoped solution‐processable TADF emitters, indicating the great potential of these materials as deep‐blue luminogens in OLED applications.  相似文献   

15.
    
The photochemistry of suprofen (SPF) was investigated by femtosecond transient absorption (fs‐TA), resonance Raman (RR) and nanosecond time‐resolved resonance Raman (ns‐TR3) spectroscopic methods to gain additional information so as to better elucidate the possible photochemical reaction mechanism of suprofen in several different solvents. In neat acetonitrile (MeCN), the fs‐TA and ns‐TR3 experimental data indicated that the lowest lying excited singlet state S1 (nπ*) underwent an efficient intersystem crossing process (ISC) to the excited triplet state T3 (ππ*), followed by an internal conversion (IC) process to T1 (ππ*). In the aqueous solution, a triplet biradical species (3ETK‐1) was obtained as the product of a decarboxylation process from triplet suprofen anion (3SPF−) and the reaction rate of the decarboxylation process was determined by the concentration of H2O. A protonation process for 3ETK‐1 leads to formation of a neutral species (3ETK‐3) that was directly observed by ns‐TR3 spectra, then this 3ETK‐3 species decayed via ISC process to generate final product. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

16.
    
N‐Benzylthiazolidine‐2‐thione is the key intermediate for the synthesis of pharmaceutically important compounds. A novel route for the synthesis of N‐benzylthiazolidine‐2‐thione through cycloaddition of CS2 with N‐benzylaziridine in the presence of 1,3‐di‐tert‐butylimidazolium‐2‐dithocarboxylate ( catalyst I ) has been proposed by reliable computations performed within the formalism of density functional theory. The mechanism of the proposed reaction is similar to the cycloaddition of tertiary aziridines and carbon dioxide using a recyclable catalyst that is reported to provide access to 3‐substituted 2‐oxazolidones with excellent yield. Because the rate determining step needs to surmount a high energy barrier, the reaction route has been deciphered in high boiling solvent (1, 2‐ethanediol). The highlight of the mechanistic route detailed here is that the proposed pathway is a cyclic process that is exothermic in nature with the regeneration of the catalyst and involves simple reagents. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

17.
    
Resonance Raman (RR) spectra of free‐base meso‐tetra(p‐hydroxyphenyl)porphine(THPP) were obtained with 397.9, 416 and 514 nm excitation wavelengths, and density functional calculations were carried out to help the elucidation of the photorelaxation dynamics of Soret (Bx and By bands) electronic transitions and the RR spectra of THPP. The RR spectrum indicates that the Franck–Condon (FC) region photorelaxation dynamics for the S0 → S5 excited electronic state is predominantly along the totally symmetric Cm phC stretching and the CβCβ stretchingand simultaneously along the asymmetric (CmCα)as stretching, ν(phC  C)asstretching, δ(NH)s and γ(CβH) vibrational relaxation processes, while that for S0 → S4 electronic state is predominantly along the Cm phC stretching and pyrrole breathing. The excited‐state structural dynamics of THPP determined from the RR spectra shows that internal conversion (IC) By → Bx electronic relaxation occurs in tens of femtoseconds, and the short‐time dynamics is interpreted using the time‐dependent wave packet theory and Herzberg–Teller (vibronic coupling) contributions. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

18.
    
Aluminum hydroxides are considered to be a potential abundant, low‐cost blue emissive material to construct UV‐pumped white light‐emitting diodes (WLEDs). In this work, a single‐source precursor chemical vapor decomposition method is adapted to fabricate stable, strongly emissive aluminum hydroxide phosphors with photoluminescence quantum yield of up to 69% in solid state by thermal decomposing aluminum diacetate hydroxide (Al(OH)(Ac)2) at temperatures (260–360 °C) in N2 atmosphere. It exhibits layered, amorphous structure and its emission of aluminum hydroxide is enhanced by electron‐donating surface hydroxyl groups and originates from F+ centers and carbon‐related defects contributing to UV (388 nm) and blue (450–520 nm) spectral regions, respectively. Employing the as‐fabricated aluminum hydroxides as blue phosphor and CuInS2 nanocrystals as red phosphor, high color rendering and high‐efficiency WLEDs with luminous efficiencies up to 37 lm W−1 and high color rendering index of 91 are fabricated. This is the best performance reported so far for aluminum hydroxide based LEDs.  相似文献   

19.
    
Lead‐based perovskite nanocrystals (NCs) are promising candidates for use in lighting and display applications; however, the toxicity of lead is one critical issue that needs to be solved for its commercialization. Consequently, less toxic tin and bismuth‐based perovskite NCs have been developed, but these materials exhibit low photoluminescence quantum yields (PLQYs) and large full width at half maximum (FWHM) values. Due to their similarity in size for Eu2+ and Pb2+, the more environmental‐friendly europium shows the potential to replace lead. Herein, the synthesis of Eu2+ doped CsBr NCs with an average size of 51.5 nm via a facile hot‐injection method is reported. The prepared CsBr:Eu2+ NCs exhibit an emission peak at 440 nm with an FWHM of 31 nm and PLQY up to 32.8%, which is persistent for at least 60 d. Moreover, the size and FWHM of CsBr:Eu2+ NCs can be tuned to 18.9 and 29 nm, respectively, by co‐doping of Ca2+ ions into the NCs. It is also demonstrated that the prepared CsBr:Eu2+ NCs can be employed as efficient color conversion materials for fabricating white light‐emitting diodes.  相似文献   

20.
    
The gas‐phase acidities (GA) of 2‐aryl‐2‐chloro‐1,1,1‐trifluoroethanes ( 1a ), 2‐aryl‐2‐fluoro‐1,1,1‐trifluoroethanes ( 2a ), and related compounds, XC6H4CH(Z)R where Z = Cl ( 1 ) or F ( 2 ) and R = C2F5 ( b ), t‐C4F9 ( c ), C(CF3)2C2F5 ( d ), C(CF3)2Me ( e ), Me ( f ), H ( g ), were investigated experimentally and computationally. On the basis of an excellent linear correlation (R2 > 0.99) of acidities of 1c , 1d , 1e , 1f and 2c , 2d , 2e , 2f where there is no fluorine atom at β‐position to the deprotonation site with the corrected number of fluorine atoms contained in the fluorinated alkyl group, the extent of β‐fluorine negative hyperconjugation of the CF3 and C2F5 groups (ΔGoβ‐F) was evaluated. The GAel values given by subtraction ΔGoβ‐F from the apparent GA value were considered to represent the electronic effect of the substituent X. The substituent effects on the GAel values and GA values for 1c , 1d , 1e , 1f and 2c , 2d , 2e , 2f were successfully analyzed in terms of the Yukawa–Tsuno equation. The variation of resonance demand parameter r? with the R group observed for various XC6H4CH(Z)R was linearly related to the GA (GAel) value of the respective phenyl‐substituted fluorinated alkanes. On the other hand, the corresponding correlation for the ρ values provided three lines for ArCH(Cl)R, ArCH(F)R and ArCH2R, respectively. These results supported our previous conclusion that the r? and ρ values are governed by the thermodynamic stability of the parent ion (ring substituent = H). Other factors arising from an atom bonded to the acidic center also influence the ρ value. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

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