黄光铱配合物Ir(dmppy)2(popy)的合成及光物理性能研究

设计合成了一种新的中性铱磷光配合物Ir(dmppy)2(popy),该配合物以2,4-二(3,5-二甲基苯基)吡啶为环金属配体,2-(2-羟基苯基)吡啶为辅助配体。通过核磁共振氢谱和碳谱(¹H-NMR、¹³C-NMR)确证了配合物的化学结构,采用光致发光光谱和紫外可见光谱研究了配合物的光物理性能,采用热分析研究了配合物的热稳定性。该配合物在二氯甲烷中的最大发射波长为575 nm,为黄光发射铱磷光配合物。     

离子型黄光铱磷光配合物的合成、结构及光物理性能研究

设计合成了一种新的离子型铱配合物[Ir(dmpmq)2(dtbpy)]PF6,该配合物以2-(3,5-二甲基苯基)-4-甲基喹啉为主配体,4,4''-二叔丁基-2,2''-联吡啶为辅助配体,六氟磷酸根为阴离子。通过核磁共振谱(¹H-NMR,¹³C-NMR)、质谱(MS)、单晶X射线衍射(XRD)确认了配合物的化学结构,采用光致发光光谱(PL)和紫外可见光谱(UV-Vis)对其光物理性能进行了研究。结果表明,该配合物为单斜晶系,空间群为C2/c;配合物在二氯甲烷溶液中的最大发射波长为579 nm,为典型的黄光发射离子型铱磷光配合物。     

一种喹啉类铱配合物的合成及光物理性能研究

以2-(3,5-二甲基苯基)喹啉(dmpq)为主配体,4,4''-二叔丁基-2,2''-联吡啶(dtbby)为辅助配体,合成出一种新型离子型铱配合物[Ir(dmpq)2(dtbbpy)]PF6。通过元素分析、质谱、核磁共振谱(¹H和¹³C)、红外光谱和单晶X射线衍射表征了配合物的组成和化学结构,通过光致发光光谱和紫外可见光谱研究了配合物的光物理性能,通过热重分析测试了配合物的热稳定性。结果表明,所合成的苯基喹啉类铱配合物呈稍微扭曲的八面体配合物,其发射波长为587 nm,热分解温度为380℃,具有足够的热稳定性,是一种潜在的黄光材料。     

一种离子型铱磷光配合物的合成及表征

以2-苯基吡啶(ppy)为环金属配体、4,4''-二叔丁基-2,2''-二吡啶(Dtbbpy)为N^N辅助配体,PF6^-为对阴离子,合成了一种离子型磷光配合物[Ir(ppy)2(Dtbbpy)]⁺PF6^-,产率为91.0%。通过元素分析(EA)、红外光谱(IR)、核磁共振谱(¹H-NMR和¹³C-NMR)和质谱(MS)对其组成和化学结构进行了确认和表征。采用紫外可见光谱(UV-Vis)和光致发光光谱(PL)研究了其光物理性能,该配合物在二氯甲烷中的最大发射波长为557 nm,属于黄绿光发射离子型铱磷光配合物。     

两种黄绿光铱配合物的合成及光物理性质研究

以2-苯基-6-(三氟甲基)-苯并噻唑和5,7-二氟-2-苯基苯并噻唑为主配体,分别与辅助配体三苯基膦合成了两种新型的环金属铱配合物(Ir1和Ir2)。用核磁共振氢谱(¹H-NMR)和质谱(MS)进行表征并确认其结构。用紫外吸收光谱以及荧光发射光谱研究了它们的光物理性质,Ir1和Ir2的最大发射波长分别为548和546 nm,发黄绿光,相对量子产率为41.1%和69.2%,荧光寿命分别为0.65和0.66 μs。密度泛函理论(DFT)计算表明紫外最大吸收峰和荧光发射峰均归因于MLCT/ILCT跃迁。     

铱配合物(Ir(ppy)2(SFO))的合成及结构表征

在乙二醇单乙醚介质中,将二聚体Ir2(μ-Cl2)(ppy)4和辅助配体2-噻吩甲酰三氟丙酮(SFO)在碱性条件下,加热回流反应,一步生成了铱配合物Ir(ppy)2(SFO),产率85.2%。采用核磁共振(¹H-NMR、¹³C-NMR)和质谱等分析表明产物为目标配合物。     

两种嘧啶基噻吩类磷光铱配合物的合成及表征

以2-嘧啶基噻吩(pymbt,L1)和2-嘧啶基苯并噻吩(pymbtp,L2)作为环金属化主配体,二(二苯基磷酰)亚胺(Htpip)作为O^O型辅助配体,合成了两种新型磷光金属铱配合物(pymbt)2Ir(tpip) (Ir1)和(pymbtp)2Ir(tpip) (Ir2)。通过核磁共振氢谱、质谱和元素分析对其进行了结构表征,用紫外-可见吸收光谱和荧光发射光谱进行了光物理性质的研究。结果表明,铱配合物Ir1和Ir2在溶液中的最大发射峰分别为563 nm和619 nm,为橙黄光和红光。在无水无氧二氯甲烷溶液中相对量子效率分别为6.3%和10.1%,磷光寿命为0.50 ms和0.63 ms。同时采用含时密度泛函理论(TDDFT)对配合物Ir1和Ir2的最低能量电子跃迁进行了计算,结果与实验测得的相应光谱数据对应的趋势相符。     

铱磷光配合物Ir(dfppy)2(phbudio)的合成及表征

以氯桥二聚体[Ir(dfppy)2(μ-Cl2)]2、1-苯基-1,3-丁二酮为原料合成了一种铱磷光配合物Ir(dfppy)2(phbudio),产率86.0%,并通过元素分析、核磁共振谱、质谱和红外光谱表征确认了目标产物的化学结构。通过紫外-可见吸收以及荧光光谱对其光物理性质进行测试,其常温最大发射位于522 nm处,显示发射强烈的绿光,初步推测该铱磷光配合物发射可能来自金属铱到环金属配体和辅助配体的电荷转移(MLCT)跃迁。     

一种离子型黄光铱配合物的合成、表征及性能研究

在温和的反应条件下，以2,4-二氟苯硼酸、2-氯喹啉为原料合成了一种新型离子型铱配合物，通过元素分析、红外光谱、¹H-NMR、质谱以及X单晶衍射对产物进行了结构表征。并考察了配合物的光物理性能和热稳定性能。结果表明配合物单晶结构为扭曲的八面体构型，属于三斜晶系，空间群为P-1；配合物最大发射波长为542 nm，CIEx, y坐标为(0.41, 0.57)，是一种新型的黄色发光的离子型铱磷光配合物。     

一种中性铱磷光配合物的合成及表征

合成了一种含有苯基吡啶单元的中性铱磷光配合物Ir(dfppy)2(fubudio) (dfppy:2,4-二氟苯基吡啶;fubudio:1-(2-糠酰)-1,3-丁二酮)。通过元素分析、核磁共振谱(¹H-NMR和¹³C-NMR)、质谱和红外光谱等表征手段确认了它的组成和化学结构。并采用紫外-可见吸收光谱和光致发光光谱对其光物理性质进行测试,常温下,其最大发射位于569 nm处,显示黄绿光发射。     

White polymer phosphorescent light-emitting devices with a new yellow-emitting iridium complex doped into polyfluorene

A new yellow-emitting iridium complex Ir(3-piq)₂pt with 3-phenylisoquinoline(3-piq) as cyclometalated ligand by introducing 2-(2H-1,2,4-triazol-3-yl)pyridine (pt) as ancillary ligand was synthesized. Efficient yellow polymer light-emitting devices (PLEDs) with the new iridium complex Ir(3-piq)₂pt in device structure ITO/PEDOT/PVK/Ir-complex (x%):PFO (or +PBD (30%))/Ba/Al (with or without PBD electron transports additive) were fabricated. The device doped with 4% Ir(3-piq)₂pt displayed a quantum efficiency of 9.4% (16.2 cd/A) at 5.06 mA/cm² with PBD additive. A white emission was also obtained at a doping concentration of 0.5% Ir(3-piq)₂pt with no PBD added. CIE coordinate (0.34 and 0.31) close to National Television Standards Committee (NTSC) white standard, external quantum efficiency of 2.25%, and luminance of 2250 cd/m² at applied voltage of 15 V were obtained. The results indicated that introducing triazole group based ancillary ligand into iridium complexes could enhance the electron-transporting ability of the iridium complexes.     

双[2-(对甲苯基)吡啶]乙酰丙酮合铱的合成及结构表征

以水合三氯化铱为原料,2-(对甲苯基)吡啶作环金属配体、乙酰丙酮作辅助配体合成了双[2-(对甲苯基)吡啶]乙酰丙酮合铱[(tpy)2Ir(acac)],通过质谱、氢谱、X射线单晶衍射分析表征手段确证了其分子结构。通过紫外可见光谱和光致发光光谱分析,研究了该配合物的光物理性能,在410和461 nm处有单重态和三重态吸收,在516 nm处有较强的绿光发射,表明该配合物是一种绿光材料。     

Sorption of Hg2+, Nd3+, Dy3+, and Uo 22+ ions at polysiloxane xerogels functionalized with phosphonic acid derivatives

The sorption properties of silicas with mono- and bifunctional surface layers containing the complexing fragment ≡Si(CH₂)₃NHP(S)(OC₂H₅)₂ were studied. It was found that xerogels synthesized by the solgel method (like mesoporous silicas obtained by the template method) can extract mercury(II) ions from acidified solutions (SSC up to 450 mg/g). In a nonporous xerogel with a bifunctional surface layer (≡P=S/-SH), thiol groups proved to be primary sorption sites for Hg²⁺ ions; part of the ligand groups were inaccessible to metal ions. Xerogels containing the phosphonic acid residues ≡Si(CH₂)₂P(O)(OH)₂ sorbed uranyl and lanthanide ions from their nitrate solutions. The resulting surface complexes contained two (for the UO₂²⁺ ion) or three innersphere ligand groups (for the Nd³⁺ and Dy³⁺ ions). The maximum SSCs were 340 mg/g for the uranyl ion and 120 mg/g for the lanthanide ions. Original Russian Text ? O.A. Dudarko, V.P. Goncharik, V.Ya. Semenii, Yu.L. Zub, 2008, published in Zashchita Metallov, 2008, Vol. 44, No. 2, pp. 207–212.     

Ir(mpiq)2(tmd)的合成、表征及光物理性能研究

以2-(3,5-二甲苯基)异喹啉(mpiq)作为环金属配体,2,2,6,6-四甲基庚二酮(tmd)为辅助配体合成了红光铱配合物Ir(mpiq)2(tmd),产率91.4%。采用元素分析、核磁共振谱、质谱、红外光谱及单晶X射线衍射表征了分子结构,采用紫外-可见吸收光谱和光致发光光谱研究了它的光物理性能。结果表明,该配合物呈稍微扭曲的六配位八面体配合物,为单斜晶系,C2/c空间群。在室温下最大发射波长为632 nm,为深红光发射铱磷光配合物。     

Synthesis of bicyclometalated iridium complex containing 1,3,4-oxadiazole-based picolinic acid derivative and its optoelectronic properties in polymer light-emitting devices

A picolinic acid derivative bearing an 1,3,4-oxadiazole unit and its bicyclometalated iridium complex (PhOXD)₂Ir(BuPhOXD-Pic) were synthesized and characterized, in which BuPhOXD-Pic is 5-(4′-(5″-(4-tert-butylphenyl)-1″,3″,4″-oxadiazol-2″-yl) phenyl) picolinic acid and PhOXD is 2,5-diphenyl-1,3,4-oxadiazole. The optoelectronic properties of this iridium complex were studied in the double-layer polymer light-emitting devices using a blend of poly (9,9-dioctylfluorene) and 5-biphenyl-2-(4-tert-butyl) phenyl-1,3,4-oxadiazole as a host matrix. This complex exhibited a maximum luminance efficiency of 7.7 cd/A at 5.6 mA/cm² and a peak brightness of 5288 cd/m² at 153.7 mA/cm² in the devices. Compared to the (PhOXD)₂Ir(Pic) complex, the (PhOXD)₂Ir(BuPhOXD-Pic) complex displays better optoelectronic properties in the devices. This study provides a convenient way to improve the optoelectronic properties of iridium complexes by modifying an ancillary ligand of picolinic acid (Pic) with an 1,3,4-oxadiazole unit.     

Luminescence of complex ion WO12 in Dy doped nanocrystal Gd6WO12 phosphor

Nanocrystal Gd₆WO₁₂ phosphor doped with Dy³⁺ was prepared by a co-precipitation method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and selected area electron diffraction (SAED) were used to characterize the structure and morphology of the resultant phosphor. It was found that the phosphor exists in tetragonal phase and the phosphor particles show sphere-like shape with an average size of 31 nm. In aid of excitation and emission spectra, the energy levels of the complex ion WO₁₂¹⁸⁻ were confirmed, and that the possible luminescent mechanisms for various wavelengths excitation were analyzed. The cross relaxation and energy transfer between complex ion and Dy³⁺ were discussed. The dependence of luminescent intensity and color coordinates on the excitation wavelength was also investigated.     

Sorption of Hg<Superscript>2+</Superscript>, Nd<Superscript>3+</Superscript>, Dy<Superscript>3+</Superscript>, and Uo<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack> ions at polysiloxane xerogels functionalized with phosphonic acid derivatives

The sorption properties of silicas with mono- and bifunctional surface layers containing the complexing fragment ≡Si(CH₂)₃NHP(S)(OC₂H₅)₂ were studied. It was found that xerogels synthesized by the solgel method (like mesoporous silicas obtained by the template method) can extract mercury(II) ions from acidified solutions (SSC up to 450 mg/g). In a nonporous xerogel with a bifunctional surface layer (≡P=S/-SH), thiol groups proved to be primary sorption sites for Hg²⁺ ions; part of the ligand groups were inaccessible to metal ions. Xerogels containing the phosphonic acid residues ≡Si(CH₂)₂P(O)(OH)₂ sorbed uranyl and lanthanide ions from their nitrate solutions. The resulting surface complexes contained two (for the UO ₂ ²⁺ ion) or three innersphere ligand groups (for the Nd³⁺ and Dy³⁺ ions). The maximum SSCs were 340 mg/g for the uranyl ion and 120 mg/g for the lanthanide ions.     

Color-tunable and white-light emitting lanthanide complexes based on (CexEuyTb1−x−y)2(BDC)3(H2O)4

Ce³⁺, Eu³⁺ and Tb³⁺ complexes were synthesized through facile and mild approaches with terephthalic acid (H₂BDC) as the ligand. Their chemical compositions were determined as (Ce_xEu_yTb_1−x−y)₂(BDC)₃(H₂O)₄ by elemental analysis (EA), Fourier transform infrared (FTIR) spectra and X-ray diffraction (XRD) measurements. Fluorescent properties of the as-synthesized complexes were investigated by changing the molar ratio of Ce³⁺, Tb³⁺ and Eu³⁺ ions, and the optimized ratio of 3.0:2.0:0.15 for Ce³⁺:Tb³⁺:Eu³⁺ in the complex was determined for white-light emission. Tuning on the emitting color was realized by adjusting the ratio among lanthanide ions, indicating the energy transfer process inside the complex. It was found that Tb³⁺ could sensitize the fluorescence of Eu³⁺ while its own fluorescence was quenched by the latter ion, and concentration quenching of Ce³⁺ was also observed. Fairly good thermal stability and oxidation resistance of the as-synthesized complexes were also demonstrated.