The synthesis, photoluminescence and energy transfer mechanism of a reactive Eu(III)-complex intermediate of white light phosphor

A reactive Eu(III)-complex intermediate of white light phosphor was synthesized using benzoylactone, 1,10-phenanthroline and undecylenic acid as ligands. The structure of the complex was characterized by elemental analysis and FT-IR spectra. The luminescent properties were investigated by fluorescence spectra and UV?Cvis absorption spectra. The results indicate that the complex emitted the characteristic peaks of the Eu(III) ion when being excited at 367?nm, revealing that the complex can be excited by 365?nm of ultraviolet. The energy of the highest occupied molecular orbital and the lowest unoccupied molecular orbital as well as the singlet state and triplet state energy level of the ligands were calculated with the Gaussian03 program package. Intramolecular energy transfer mechanism was studied and an energy transfer diagram was sketched to illuminate the energy transfer process. The Eu(III)-copolymer was synthesized by the free radical copolymerization of the Eu(III)-complex and methyl methacrylate. XRD analysis indicates that the Eu(III)-complex in the copolymer was dispersed much more uniformly into the polymer matrix than that in the doped polymer. The photoluminescent properties of the Eu(III)-polymer suggest that the Eu(III)-complex is a good candidate of red light moiety in white light phosphor.     

Cationic conjugated polymers for homogeneous and sensitive fluorescence detection of hyaluronidase

The cationic charged water-soluble polyfluorenes containing 2,1,3-benzothiadiazole (BT) units (P1–3) have been synthesized and characterized. These polymers demonstrate intramolecular energy transfer from the fluorene units to the BT sites when oppositely charged hyaluronan is added due to the formation of electrostatic complexes, followed by a shift in emission color from blue to green or brown. Upon adding hyaluronidase, the hyaluronan is cleaved into fragments. The relatively weak electrostatic interactions of hyaluronan fragments with polyfluorenes keep their main chains separated and energy transfer from the fluorene units to the BT sites is inefficient, and the polyfluorenes recover their blue emissions. The complexes of conjugated polymers/hyaluronan can be utilized as probes for sensitive and facile fluorescence assays for hyaluronidase. The new assay method interfaces with the aggregation and light harvesting properties of conjugated polymers. Supported by the “100 Talents” Program of Chinese Academy of Sciences, the National Natural Science Foundation of China (Grant Nos. 20725308 & 20721061), and 973 Project (Grant Nos. 2006CB806200 & 2006CB932100)     

Electrochemically controllable emission and coloration by using europium(III) complex and viologen derivatives

We have demonstrated electroswitchable emission and coloration using a novel composite material containing luminescent europium(III) complex Eu(hfa)(3)(H(2)O)(2) and diheptyl viologen HV(2+). The photoluminescence of the Eu(III) complex was controlled by the electrochemical coloration of HV(2+)via intermolecular energy transfer mechanisms.     

A NOVEL SUPRAMOLECULAR CLATHRATE OF RODLIKE p-BUTOXYBENZYLIDENE-p′-DODECOXYANILINE TRAPPED WITHIN POLYORGANOSILOXANE PORE*

A novel supramolecular polysiloxane clathrate, POS/C, has been preparedby in-situ encapsulating rodlike p-butoxybenzylidene-p ' - dodecoxyaniline (BBDA ) , one kindof Schiff base liquid crystal molecule, within the pore of polyorganosiloxane (POS) whichis prepared by hydrosilylation coupling reaction of polyvinylsilsesquioxane (Vi- T ) withtetramethyldisiloxane (H-MM). Investigation by polarized light microscopy (PLM), differ-ential scanning calorimetry (DSC), infrared spectroscopy (IR), atomic force microscopy(AFM) and molecular simulation gives a preliminary support to the existence of the titlesupramolecular clathrate.     

d → f energy transfer in a series of Ir(III)/Eu(III) dyads: energy-transfer mechanisms and white-light emission

An extensive series of blue-luminescent iridium(III) complexes has been prepared containing two phenylpyridine-type ligands and one ligand containing two pyrazolylpyridine units, of which one is bound to Ir(III) and the second is pendant. Attachment of {Ln(hfac)(3)} (Ln = Eu, Gd; hfac = anion of 1,1,1,5,5,5,-hexafluoropentanedione) to the second coordination site affords Ir(III)/Ln(III) dyads. Crystallographic analysis of several mononuclear iridium(III) complexes and one Ir(III)/Eu(III) dyad reveals that in most cases the complexes can adopt a folded conformation involving aromatic π stacking between a phenylpyridine ligand and the bis(pyrazolylpyridine) ligand, but in one series, based on CF(3)-substituted phenylpyridine ligands coordinated to Ir(III), the steric bulk of the CF(3) group prevents this and a quite different and more open conformation arises. Quantum mechanical calculations well reproduce these two types of "folded" and "open" conformations. In the Ir(III)/Eu(III) dyads, Ir → Eu energy transfer occurs with varying degrees of efficiency, resulting in partial quenching of the Ir(III)-based blue emission and the appearance of a sensitized red emission from Eu(III). Calculations based on consideration of spectroscopic overlap integrals rule out any significant contribution from F?rster (dipole-dipole) energy transfer over the distances involved but indicate that Dexter-type (exchange) energy transfer is possible if there is a small electronic coupling that would arise, in part, through π stacking between components. In some cases, an initial photoinduced electron-transfer step could also contribute to Ir → Eu energy transfer, as shown by studies on isostructural iridium/gadolinium model complexes. A balance between the blue (Ir-based) and red (Eu-based) emission components can generate white light.     

The influence of triplet energy levels of bridging ligands on energy transfer processes in Ir(III)/Eu(III) dyads

A series of N^N,O^O-bridging ligands based on substituted 1-(pyridin-2-yl)-3-methyl-5-pyrazolone and their corresponding heteroleptic iridium(III) complexes as well as Ir-Eu bimetallic complexes were synthesized and fully characterized. The influence of the triplet energy levels of the bridging ligands on the energy transfer (ET) process from the Ir(III) complexes to Eu(III) ions in solution was investigated at 77 K in Ir(III)/Eu(III) dyads. Photophysical experiment results show the bridging ligands play an important role in the ET process. Only when the triplet energy level of the bridging ligand was lower than the triplet metal-to-ligand charge transfer ((3)MLCT) energy level of the Ir moiety, was pure emission from the Eu(III) ion observed, implying complete ET took place from the Ir moiety to the Eu(III) ion.     

Repair of Pd/α-Al2O3 composite membrane with defects

A palladium composite membrane with a large number of defects was repaired using the electroless plating combined with the technique of osmosis. The loose structure of palladium film prepared by the conventional electroless plating was densified. Defects were repaired. Hydrogen selectivity was thus significantly increased without significantly increasing palladium film thickness and reducing hydrogen permeability. Project supported by the Chinese Academy of Sciences (Grant No. KJ951-A1-508) and the National Natural Science Foundation of China (Grant No. 29392003).     

THE IMPORTANCE OF COMPLEX FORMATION IN THE SENSITIZATION OF Eu(III) EMISSION BY OROTIC ACID

Abstract— Orotic acid (I) and 3-methylorotic acid (II) are the only orotic acid derivitives which efficiently sensitire emission from Eu(III) in D₂O solution. This emission is only weakly sensitized by I-methylorotic acid (III), 1,3-dimethylorotic acid (IV), the methyl and isopropyl esters of orotic acid (V) 6-acetyluracil (VI) and not sensitized at all by the bases uracil. thymine and their nucleosides. Substituent groups on either the carboxyl group or the N-l position of the ring thus prevent efficient energy transfer from the excited orotic acid to Eu(III). These structural requirements for efficient energy transfer are the same as the structural requirements for formation of a stable. bidentate. ground state complex between Eu(III) and orotic acid (VII) (Sarpotdar and Burr, 1978).
We, therefore, propose that sensitization of Eu(III) emission by orotic acid at pH 5 is an example of energy transfer within the bidentate complex of Eu(III) and orotic acid. We also propose that the complexed orotic acid is itself excited by eollisional energy transfer from free triplet excited orotic acid (since the concentration of complex measured to be present. 5–7%, is too low to account for the efficiency of the sensitization). We also propose that emission from the excited complexed Eu(III) can be either from the complexed ion or from free Eu(III)* resulting from dissociation of the complex during the lifetime of the excited ion.
The efficiency of Eu(III) sensitized emission is shown to depend on the concentrations of Eu(III). orotic acid and pH with relationships kinetically consistent with the above hypothesis.     

Electronic spectroscopy and photochromic mechanism of bis-Schiff bases, N, N′-bis(2-hydroxy-l-naphthylidene)-l, 4-phenyldiamine

The steady state and transient state absorption spectra and fluorescence spectra of N, Ń-bis(2-hydroxy-1-naphthylidene)-1, 4-phenyldiamine (BNP) in cyclohexane and acetonitrile were determined. The photochromic mechanism was discussed. In nonpolar solvents, BNP exists mainly in the enol form and has the absorption maximum in the UV region. In polar solvents, however, both the enol and proton transfer tautomer are formed, but the former is the main one. Fluorescence emissions result from the excited state of proton transfer product. Project supported by the National Natural Science Foundation of China and the Foundation of Chinese Academy of Sciences.     

Discussions about whether radioactive half life can be changed by mechanic motion

In this essay, some discussions and comments about the paper entitled “Can the decay rate of ³²P be changed by mechanic motion?” (Ding et al., Science in China Series B: Chemistry (Chinese version), 2008, 38(11):1035–1037) are given. It was strongly suggested that its experimental methods, data calculations and conclusion should be reconsidered. After the data were recalculated, the new results supported that the chiral mechanic motion could induce the changes of radioactive half life. Supported by the National Natural Science Foundation of China (Grant Nos. 20571085, and 20877099), Fund of the President of Chinese Academy of Sciences (Grant No. 0521021T04), 2005/2006 USA Li’s Foundation Merit Prize Fund, Fund of Graduate University of Chinese Academy of Sciences (Grant No. 065101HM03), and Fund of the Key Laboratory of Nuclear Analysis of the Institute of High Energy Physics of Chinese Academy of Sciences (Grant No. K129)     

Theoretical studies on intratriplex DNA with 5-bromocytosine

ＯｌｉｇｏｎｕｃｌｅｏｔｉｄｅｃａｎｒｅｃｏｇｎｉｚｅｔｈｅｍａｊｏｒｇｒｏｏｖｅｏｆｄｏｕｂｌｅｈｅｌｉｃａｌＤＮＡａｔｓｐｅｃｉｆｉｃｓｅｑｕｅｎｃｅｓｂｙｆｏｒｍｉｎｇＨｏｏｇｓｔｅｅｎｏｒｒｅｖｅｒｓｅＨｏｏｇｓｔｅｅｎｈｙｄｒｏｇｅｎｂｏｎｄｓｗｉｔｈｐｕｒｉｎｅｂａｓｅｓｏｆｔｈｅＷａｔｓｏｎＣｒｉｃｋｂａｓｅｐａｉｒｓ,ｒｅｓｕｌｔｉｎｇｉｎａｔｒｉｐｌｅｈｅｌｉｘ[1].Ｔｒｉｐｌｅｈｅｌｉｘｆｏｒｍｉｎｇｏｌｉｇｏｎｕｃｌｅｏｔｉｄｅｓｃａｎｂｅｕｓｅｄｔｏｓｅｌｅｃｔｉｖｅｌｙｃ…     

Mechanism of activation and catalysis of chemiluminescence by Eu(fod)3 chelate in thermal decomposition of adamantylideneadamantane-1,2-dioxetane

Complexation of the chelate both with dioxetane and with adamantanone (2), the product of decomposition of dioxetane, have an important effect on chemiluminescence (CL) in thermal decomposition of adamantylideneadamantane-1,2-dioxetane (1) in the presence of Eu(fod)₃ chelate. The stability constants of Eu(fod)₃·1 and Eu(fod)₃·2 complexes were obtained. It was found that Eu(fod)₃ catalyzes and activates chemiluminescent decomposition of1. The rate constant (k₂) of decomposition of the Eu(III)·1 complex was determined from the kinetics of quenching of CL, and the activation parameters were determined from the temperature curve. Luminescence from the⁵D_1-level of the Eu(III) ion was detected in the CL spectrum and was correlated with direct (bypassing the triplet of the ligand) transfer of excitation energy from2 _t* to the luminescent levels of Eu(III) in the geometrically distorted complex Eu(fod)₃·2.Institute of Organic Chemistry, Ural Branch, Russian Academy of Sciences, 450054 Ufa. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1056–1063, May, 1992.     

A schiff-base bibracchial lariat ether forming a cryptand-like cavity for lanthanide ions

We report here a structural and photophysical study of lanthanide(III) complexes with the di-deprotonated form of the bibracchial lariat ether N,N'-bis(2-salicylaldiminobenzyl)-1,10-diaza-15-crown-5. The X-ray crystal structures of [Ce(L(2)-2H)](ClO(4)).0.5H(2)O (2) and [Sm(L(2)-2H)](ClO(4)).C(3)H(8)O (5b) show the metal ion being nine-coordinated and deeply buried in the cavity of the dianionic receptor. Thanks to the formation of a pseudomacrocycle through pi-pi interaction between one of the phenol rings and one of the benzyl rings, the complexes present a cryptand-like structure in the solid state. (1)H and (13)C NMR studies on the La(III) complex point that the solid state structure is essentially maintained in acetonitrile solution. High-resolution laser-excited emission spectra of the crystalline Eu(III) complex demonstrate the presence of several coordination sites arising from different conformations of the crown moiety. The ligand-to-Eu(III) energy transfer is relatively efficient at low temperature, but back transfer is implied in the deactivation process, especially at room temperature, because the ligand triplet state lies at very low energy. However, the low energy of the (3)pipi state provides an efficient conversion of the visible light absorbed into near-infrared light emitted by the Nd(III) ion.     

Effects of charge distribution on water filling process in carbon nanotube

Using umbrella sampling technique with molecular dynamics simulation, we investigated the nanofluidic transport of water in carbon nanotube (CNT). The simulations showed that a positive charge modification to the carbon nanotube can slow down the water column growth process, while the negative charge modification to the carbon nanotube will, on the other hand, quicken the water column growth process. The free energy curves were obtained through the statistical process of water column growth under different charge distributions, and the results indicated that these free energy curves can be employed to explain the dynamical process of water column growth in the nanosized channels. Supported by the National Natural Science Foundation of China (Grant Nos. 10425420 and 20773145), the Ministry of Science and Technology of China (Grant Nos. 2006CB806200 and 2006CB932100), and the Chinese Academy of Sciences including its CNIC Supercomputer Center.     

Ligand-passivated Eu:Y2O3 nanocrystals as a phosphor for white light emitting diodes

Eu(III)-doped Y(2)O(3) nanocrystals are prepared by microwave synthetic methods as spherical 6.4 ± 1.5 nm nanocrystals with a cubic crystal structure. The surface of the nanocrystal is passivated by acetylacetonate (acac) and HDA on the Y exposed facet of the nanocrystal. The presence of acac on the nanocrystal surface gives rise to a strong S(0) → S(1) (π → π*, acac) and acac → Ln(3+) ligand to metal charge transfer (LMCT) transitions at 270 and 370 nm, respectively, in the Eu:Y(2)O(3) nanocrystal. Excitation into the S(0) → S(1) (π → π*) or acac → Ln(3+) LMCT transition leads to the production of white light emission arising from efficient intramolecular energy transfer to the Y(2)O(3) oxygen vacancies and the Eu(III) Judd-Ofelt f-f transitions. The acac passivant is thermally stable below 400 °C, and its presence is evidenced by UV-vis absorption, FT-IR, and NMR measurements. The presence of the low-lying acac levels allows UV LED pumping of the solid phosphor, leading to high quantum efficiency (～19%) when pumped at 370 nm, high-quality white light color rendering (CIE coordinates 0.33 and 0.35), a high scotopic-to-photopic ratio (S/P = 2.21), and thermal stability. In a LED lighting package luminosities of 100 lm W(-1) were obtained, which are competitive with current commercial lighting technology. The use of the passivant to funnel energy to the lanthanide emitter via a molecular antenna effect represents a new paradigm for designing phosphors for LED-pumped white light.     

Microwave-assisted sensing of tetracycline using europium-sensitized luminescence fibers as probes

In this paper, we describe a facile approach—using silicate fibers immobilized with Eu(III) ions [Eu(III) fibers] as affinity probes—to rapidly sense tetracycline (TC) in complex samples. The fabrication of the Eu(III) fibers is straightforward: Simply immerse a silicate fiber into a glass tube containing Eu(III) and irradiate with microwaves (power, 900 W) for 30 s. The Eu(III) fibers selectively trap TC from aqueous samples via chelation of the β-diketone functional group of TC with the Eu(III) center. Because the Eu(III)–TC complexes on the fibers are luminescent, as a result of intermolecular energy transfer from the TC moieties to the Eu(III) centers, they can be detected directly using a fluorophotometer. To accelerate the sensing process, we also used microwave irradiation (for only 15 s) to trap the TC molecules from the sample solutions onto the Eu(III) fibers. Furthermore, only a small volume (< 10 μL) of sample solution is required for these analyses. This approach allows TC to be detected in aqueous samples, with a detection limit of 50 nM.     

Tuning the triplet energy levels of pyrazolone ligands to match the 5D0 level of europium(III)

Three pyrazolone-based ligands, namely 1-phenyl-3-methyl-4-(1-naphthoyl)-5-pyrazolone (HL1), 1-phenyl-3-methyl-4-(4-dimethylaminobenzoyl)-5-pyrazolone (HL2), and 1-phenyl-3-methyl-4-(4-cyanobenzoyl)-5-pyrazolone (HL3), were synthesized by introducing electron-poor or electron-rich aryl substituents at the 4-position of the pyrazolone ring. Their corresponding europium complexes Eu(LX)3(H2O)2 and Eu(LX)3(TPPO)(H2O) (X = 1-3) were characterized by photophysical studies. The characteristic Eu(III) emission of these complexes with at most 9.2 x 10(-3) of fluorescent quantum yield was observed at room temperature. The results show that the modification of ligands tunes the triplet energy levels of three pyrazolone-based ligands to match the 5D0 energy level of Eu3+ properly and improves the energy transfer efficiency from antenna to Eu3+, therefore enhancing the Eu(III) emission intensity. The highest energy transfer efficiency and probability of lanthanide emission of Eu(L1)3(H2O)2 are 35.1% and 2.6%, respectively, which opens up broad prospects for improving luminescent properties of Eu(III) complexes by the modification of ligands. Furthermore, the electroluminescent properties of Eu(L1)3(TPPO)(H2O) were also investigated.     

Photoluminescent dinuclear lanthanide complexes with tris(2-pyridyl)carbinol acting as a new tetradentate bridging ligand

A tripodal ligand, tris(2-pyridyl)carbinol, affords a novel tetradentate coordination mode in homodinuclear lanthanide complexes, which exhibit remarkably short distances between metal ions. The strong luminescences of Eu(III) and Tb(III) complexes with the ligand demonstrate that the ligand has a suitable excited state for energy transfer from the ligand to the Eu(III) and Tb(III) centers, respectively.     

等离子体共振协同S-scheme电荷转移促进W18O49/Cd0.5Zn0.5S高效光催化产氢

硫化锌镉(Cd_1-xZn_xS,01-xZn_xS太阳光响应范围,提高光生电子与空穴利用效率是当前的研究热点.本文采用溶剂热法分别制备了Cd_0.5Zn_0.5S纳米棒和W₁₈O₄₉纳米颗粒,然后借助超声辅助静电自组装策略成功获得具有紫外-可见-近红外光响应的W₁₈O₄₉/Cd_0.5Zn_0.5S异质结.分析表明,W₁₈O₄₉晶格氧空位周围过量自由电荷的集体振荡,引起强烈的局域表面等离子体共振(LSPR)吸收现象,使其对500~800 nm范围的光产生明显吸收,使体系具有紫外至近红外光响应能力;而且W₁₈O₄₉作为一种氧化型半导体材料,可与还原型Cd_0.5Zn_0.5S半导体之间形成S-scheme异质结,在内建电场、能带弯曲和静电相互作用下有效促进了光生电子和空穴的分离,并能保留强的氧化还原能力.对比实验发现,常温下以Na₂S/Na₂SO₃为牺牲剂,全光谱照射下,20%-W₁₈O₄₉/Cd_0.5Zn_0.5S的产氢速率可达147.7mmol·g^-1·h^-1,是Cd_0.5Zn_0.5S纳米棒单体的2.1倍;可见光下,复合样品的产氢活性约为Cd_0.5Zn_0.5S单体的1.89倍;近红外光下,Cd_0.5Zn_0.5S单体无产氢活性,而异质结的产氢速率约为0.2 mmol·g^-1·h^-1.进一步对样品波长依赖性研究发现,当365、400、450 nm的入射光仅能引起W18O49和Cd0.5Zn0.5S的带间激发时,它们的复合样品比Cd_0.5Zn_0.5S表现出更优异的产氢活性;当λ=550、600、650 nm以及>800 nm的入射光仅能引起W₁₈O₄₉的LSPR效应时,Cd_0.5Zn_0.5S单体无活性,而W₁₈O₄₉/Cd_0.5Zn_0.5S仍具有较高的催化性能、但随着波长的增大产氢速率逐渐降低,与复合样品瞬态光电流强度的变化趋势吻合良好.以上结果表明,W₁₈O₄₉与Cd_0.5Zn_0.5S二者形成的S-scheme界面异质结有效抑制了光生载流子的表面复合,且当入射光不足以引起带间激发时,W₁₈O₄₉的LSPR效应产生的"热电子"可有效注入到Cd_0.5Zn_0.5S,从而引起表面催化反应.进一步研究发现,当将反应温度从25提高到60°C时,20%-W₁₈O₄₉/Cd_0.5Zn_0.5S在全光谱下的产氢速率可提高到306.1mmol·g^-1·h^-1,表明温度对光催化产氢过程具有不可忽视的影响,可通过增强表面反应速率显著提高产氢活性.总之,本文通过一种简便方法获得了具有紫外-可见-近红外响应的S型W₁₈O₄₉/Cd_0.5Zn_0.5S异质结光催化剂,详细对比了不同波段下样品的光电特性及催化活性,最终在S-scheme电荷转移机制和LSPR"热电子"注入过程的协同作用下,复合样品活性比Cd_0.5Zn_0.5S单体有了明显提高.     

Luminescent sol–gel materials based on lanthanide aminopolycarboxylates (Ln = Nd, Eu, Tb, Yb)

Luminescent organic–inorganic hybrid materials containing immobilized lanthanide(III) complexes (Ln = Nd, Eu, Tb, Yb) with modified ethylenediaminetetraacetic and diethylenetriaminepentaacetic acid were synthesized by sol–gel method. Obtained hybrids exhibit 4f-luminescence in the visible (Eu(III) and Tb(III)) and IR-region (Nd(III) and Yb(III)). The influence of the hybrid matrix on the lanthanide luminescence was established and it was shown, that the location of resonance level of Eu(III) is optimal for efficient energy transfer from matrix, while in the case of Tb(III) energy transfer does not occur and Tb(III) is able to absorb energy only due to its own week f–f transitions. It was also established that the inorganic matrix leads to elimination of nonradiative energy losses and increase of 4f-luminescence lifetimes. Covalent binding of Ln(III) aminopolycarboxylates in the matrix allows to consider obtained materials as promising for creation of photo- and chemically-stable luminescent sensors.