Zn(BTZ)2白色有机电致发光材料的合成及其器件制备

以PCl₃为脱水剂,将邻氨基硫酚与水杨酸脱水环化合成出2-(2-羟基苯基)苯并噻唑,并进一步将所得产物与乙酸锌反应合成出2-(2-羟基苯基)苯并噻唑螯合锌(Zn(BTZ)₂)材料。以该配合物作为发光层制备出结构为ITO/PVK:TPD/Zn(BTZ)₂/Al近白色电致发光器件,其色坐标位于白场之内(x=0.242,y=0.359),在驱动电压为16V时,亮度达3200cdm²,对应的量子效率为0.32%。进一步在Zn(BTZ)₂中掺入橙红色染料Rubrene,制成ITO/PVK:TPD/Zn(BTZ)₂:Rubrene/Al结构器件,实现了纯白色发光(色坐标值:x=0.324,y=0.343),非常接近于白色等能点,且量子效率达0.47%。最后对上述器件的发光和电学性能进行了深入的研究和探讨。     

Chelate polymers: II. Some novel transition metals complexes with azomethine‐containing siloxanes and their polyesters

New Schiff bases of 2,4‐dihydroxybenzaldehyde with siloxane‐α,ω‐diamines having different numbers of siloxane units in the chain have been synthesized and characterized by spectroscopy, elemental and thermal analyses. These azomethines were found to form complexes readily with copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). From IR and UV–Vis studies, the phenolic oxygen and imine nitrogen of the ligand were found to be the coordination sites. Thermogravimetric analysis (TGA) data indicate the chelates to be more stable than the corresponding ligands. The melting points increase with shortening of the siloxane segment from azomethine, as well as the result of complexation. The chelates obtained were covalently inserted in polymeric linear structures by polycondensation through the OH‐difunctionalized ligand with 1,3‐bis(carboxypropyl)tetramethyldisiloxane. Direct polycondensation, assisted either by acetic anhydride or N,N′‐dicyclohexylcarbodiimide as dehydrating agent and the complex 4‐(dimethylamino)pyridinium 4‐toluenesulfonate as catalyst, was used for the synthesis of these compound types. The structures of the polymers obtained were confirmed by IR, UV and ¹H NMR. Characterization was undertaken by TGA, solubility tests and viscosity measurements. Copyright © 2003 John Wiley & Sons, Ltd.     

Diene complexes of early transition metals: ideas and progresses at Osaka University

Historical perspectives for the chemistry of diene complexes of early transition metals developed at Osaka University in the period after 1970s were reviewed briefly and personally. Preparative chemistry of this field commenced from the magnesium-diene 1:1 compounds and quickly extended to almost all the early transition metals. By the studies operated together with other researchers, unique features of these diene complexes, especially their bonding and structure, selective reactions, and catalysis performances are described.     

Synthesis and luminescence properties of lanthanide(III) chelates with polyacid derivatives of thienyl-substituted terpyridine analogues

Two new polyacid derivative ligands of thienyl-substituted terpyridine analogues, N,N,N¹,N¹-[4′-(2?-thienyl)-2,2′:6′,2″-terpyridine-6,6″-diyl]bis(methylenenitrilo) tetrakis(acetic acid) (TTTA) and N,N,N¹,N¹-[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-(2″-thienyl)pyridine] tetrakis(acetic acid) (BTTA), were synthesized, and the luminescence properties of their Eu³⁺ and Tb³⁺ chelates were investigated. The Eu³⁺chelates of the two ligands are strongly luminescent having luminescence quantum yields of 0.150 (TTTA-Eu³⁺) and 0.114 (BTTA-Eu³⁺), and lifetimes of 1.284 ms (TTTA-Eu³⁺) and 1.352 ms (BTTA-Eu³⁺), whereas their Tb³⁺ chelates are weakly luminescent. The TTTA-Eu³⁺ chelate was used for streptavidin (SA) labeling, and the labeled SA was used for time-resolved fluoroimmunoassay of insulin in human sera. The method gives the detection limits of 33 pg ml⁻¹.     

1,3-diallyl-5-[ω-(diphenylphosphino)alkyl] isocyanurates in reactions of complex formation with palladium(ii) dichloride

The reactions of phosphine derivatives of diallyl isocyanurates with palladium(ii) dichloride lead to the formation of complexes, whose structure, composition, and stability depend on the length of the methylene chain between the isocyanurate and diphenylphosphine fragments in the ligand. 1,3-Diallyl-5-[5′-(diphenylphosphino)pentyl and 10′-(diphenyl-phosphino)decyl] isocyanurates with PdCl₂ form monomeric L₂PdCl₂ trans-complexes in which P atoms of the ligands participate in coordination with the metal. 1,3-Diallyl-5-[2′-(diphenylphosphino)ethyl] isocyanurate with PdCl₂ forms a dimeric (LPdCl₂)₂ complex, which decomposes in a solution to the monomer including solvent molecule into the coordination sphere of the metal. The reactions of 1,3-diallyl-5-[4′-(diphenylphosphino)butyl] isocyanurate and 1,3-diallyl-5-[6′-(diphenylphosphino)hexyl] isocyanurate with PdCl₂ give monomeric chelate LPdCl₂ complexes in which one of the allyl groups of the isocyanurate cycle participates in coordination with the central ion along with the phosphorus atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1859–1865, September, 1998.     

Potentiometric studies on the complexation equilibria between some trivalent lanthanide metal ions and biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS)

Summary The chelation behaviour of some trivalent lanthanide and yttrium metal ion with biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS) has been investigated by potentiomotric measurements at 20±0.5°C in 75% (v/v) dioxane-water medium at various ionic strengths of sodium perchlorate. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of (average number of ligand bound per metal ion) andpL (free ligand exponent). The formation constants of metal chelates have been computed on a PC-XT computer, using a program patterned after that of Sullivan et al. to give _n values using weighted least squares method. TheS _min values (S _min =²) have been calculated. The order of formation constants of chelates was found to be: La³⁺3+3+3+3+3+3+3+3+3+. The formation constants of the chelates formed have been correlated to size and ionization potentials of the metal ions.

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Potentiometrische Untersuchungen der Komplexierungsgleichgewichte zwischen einigen trivalenten Metallionen und biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS)

Zusammenfassung Es wurde das Chelierungsverhalten einiger trivalenter Lanthanidenionen mit biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS) mittels potentiometrischer Messungen bei 20±0.5°C in 75% (v/v) Dioxan-Wasser bei verschiedener Ionenstärke an Natriumperchlorat untersucht. Die Methode nach Bjerrum und Calvin in der Modifikation nach Irving und Rossotti wurde zur Ermittlung der Werte (mittlere Anzahl an Liganden pro Metallion) undpL (Exponent an freiem Liganden) verwendet. Die Komplexbildungskonstanten wurden in Anlehnung an Sullivan et al. an einem PC-XT Computer errechnet. DieS _min-Werte (S _min=²) wurden ebenfalls bestimmt. Die Reihung der Chelatbildungskonstanten war: La³⁺3+3+3+3+3+3+3+3+3+. Die Bildungskonstanten sind mit der Größe und dem Ionisierungspotential der Metallionen zu korrelieren.

     

Boron chelates with 5,5,5-trifluoro- and 5,5,5-trichloro-4-aminopent-3-en-2-ones

Boron chelates were obtained by the reaction of butoxy(butylthio)diphenylborane with 5,5,5-trifluoro(trichloro)-4-aminopent-3-en-2-one, and their reactions with primary amines were investigated. -Diiminate complexes of boron with trifluoro- and trichloromethyl groups were synthesized.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2657–2661, November, 1992.     

镧系离子与L-羟脯氨酸、DL-瓜氨酸配位作用研究

稀土与体内广泛存在的生物配体氨基酸的配位作用，尤其是三元体系的研究对于阐明稀土元素在体内的存在形态及探索稀土生物效应具有重要意义．羟脯氨酸和瓜氨酸均是人体中存在的重要氨基酸，它们在人体血浆中的浓度与必需的氨基酸相近［‘j．稀土与氨基酸配位作用的研究已有较多报道「’‘，但模拟生理条件下稀土离子与羟脯氨酸、瓜氨酸的二元、三元配合物的PH电位法研究尚未见报道．本文报道在模拟生理条件下（37C，0·15mol／LNaCI）湖系离子（Pm和Lu除外）与上述2种氨基酸的二元及三元配合物PH电位法研究结果．1实验部分1．1试剂和仪…     

Zur Elektronenstruktur metallorganischer Komplexe der f‐Elemente. 64 Äußert sich die zwitterionische Natur des Triphenylphosphanoxid‐Liganden auch in seinen spektrochemischen Eigenschaften?

Electronic Structures of Organometallic Compounds of f Elements. 64 Does the Zwitterionic Nature of the Triphenylphosphine Oxide Ligand Manifest itself in its Spectrochemical Properties? The triphenylphosphine oxide mono adducts of the moiety tris(η⁵‐cyclopentadienyl)lanthanide(III) (Ln(Cp)₃; Ln = Pr ( 1 ), La ( 2 )) were synthesized and structurally characterized. The Ln–O distances of these compounds are noticeably shorter than those of the corresponding THF adducts. A crystal field (CF) analysis of the optical spectra of 1 leads to a low absolute value of the quadratic CF parameter which is comparable with those of [Pr(Cp)₃(L)]^? adducts with anionic bases but not with [Pr(Cp)₃(MeTHF)]. Reasons for the latter finding are presented.