两种离子型铱配合物的合成、光物理性质及对OH-的检测

以两种2,2’-联吡啶衍生物为中性配体，2-(3-氟苯基)吡啶为环金属配体，合成了两种新型的离子型Ir(Ⅲ)配合物Ir1和Ir2。利用核磁、质谱和晶体结构分析确认了配合物Ir1和Ir2的结构。配合物Ir1和Ir2在CH2Cl2溶液中的最大发射波长分别为570和528 nm，为橙红光和黄光。两种配合物在无氧CH2Cl2溶液中的量子产率分别为0.88和0.57，磷光寿命分别为2.43和2.40 μs。通过理论计算详细讨论了中性配体的取代基种类对其光谱性质的影响。在配合物Ir1的DMSO/H2O溶液中加入OH^-后，其发射峰强度提高了近100倍，溶液的发光颜色由红色变为明亮的绿色，检出限为8.47×10^-6 mol/L。机理研究表明，OH^-取代了Ir1的中性配体上的溴取代基，形成了新的含有羟基的配合物，从而改变了Ir1的光谱特性，实现对OH^-的高选择性和高灵敏度检测。     

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。     

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。     

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。     

两种新型铱(Ⅲ)配合物的合成与性质研究

分别以2-苯基吡啶(ppy)为第一配体,以1-苯基-1,3-丁二酮(phbd),1-苯基-3-甲基-4-苯甲酰基-吡唑啉酮-5(pmbp)为第二配体合成了两个新的铱配合物Ir(ppy)2(pmbp)、Ir(ppy)2(phbd),通过红外光谱、元素分析和核磁共振对其化学组成进行了结构表征,表征结果与理论吻合良好;配合物在紫外吸收光谱图上的290~310 nm处出现了强的配体自旋允许的单重态π-π*跃迁吸收峰,在400~460 nm处出现了配合物分子内金属铱到配体的单重态和三重态电荷跃迁吸收峰(1MLCT和3MLCT);同时配合物Ir(ppy)2(pmbp)、Ir(ppy)2(phbd)在荧光光谱上522、518 nm处出现了强的绿光发射。     

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。     

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。     

一种红光铱配合物的合成、晶体结构及性能

以1-苯基异喹啉(piq)为主配体，以3-甲基-2-吡啶甲酸(mecid)为辅助配体合成了一种铱(Ⅲ)配合物Ir(piq)₂(mecid)。采用元素分析、红外光谱、核磁共振谱分析和单晶X射线衍射对其化学组成和结构进行了表征。采用热失重(TGA)曲线分析了其热稳定性质，热分解温度为325℃。采用紫外-可见光谱和光致发光光谱对其光物理性质进行了分析。结果表明，化学组成为C₃₇H₂₆Ir N₃O₂，属于三斜晶系，P₁/n空间群。晶胞参数为a=8.3130(4) nm,b=11.4866(5) nm,c=15.3737(7) nm,α=75.726(2)°，β=83.005(2)°，γ=88.785(2)°，V=1.4120(11) nm³,Z=2。光物理性质显示最大发射波长为618 nm，为红色发射的铱磷光配合物。     

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。     

蓝光铱配合物的合成、结构表征及光物理性能测试

在碱性条件下,以铱的氯桥二聚体(dfppy)2Ir(μ-Cl2)Ir(dfppy)2和乙酰丙酮反应合成出高效磷光材料二[2-(2,4-二氟苯基)吡啶-C2,N'](乙酰丙酮)合铱(III)(Ir(dfppy)2(acac))。用核磁共振谱(1H NMR、13C NMR)、红外光谱和单晶X射线衍射等表征手段确定了分子结构,用高效液相色谱法测定了纯度,用光致发光光谱测试了光物理性能。结果表明,合成的配合物组成及结构与实际一致,Ir(dfppy)2(acac)为电中性八面体配合物,Ir-O、Ir-C、Ir-N键的平均长度分别为0.2160(14)、0.1998(11)、0.2030(15)nm,在484 nm处出现了较强的蓝光发射。方法的合成产率大于90%,纯度99.70%,适于批量制备。     

Toward the saturated red phosphorescence for OLED: New iridium complexes of 2,3-bis(4-fluorophenyl)quinoxaline derivatives

For development of an optimized red dopant in the organic light emitting devices (OLEDs), new iridium complexes containing 2,3-dpqx derivatives as a ligand were prepared. The ligands were prepared according to Friedlander reaction. The complexes, Ir(2,3-dpqx-F₂)₂(acac) (2,3-dpqx-F₂ = 2,3-bis(4-fluorophenyl)-quinoxaline; acac = acetylacetonate) and Ir(6-Me-2,3-dpqx-F₂)₂(acac) (6-Me-2,3-dpqx-F₂ = 2,3-bis(4-fluorophenyl)-6-methylquinoxaline) were synthesized from the two-step reactions of IrCl₃·xH₂O with the corresponding ligand and characterized by ¹H NMR, mass spectrometry and elemental analysis. Ir(2,3-dpqx-F₂)₂(acac) and Ir(6-Me-2,3-dpqx-F₂)₂(acac) exhibited the luminescence peaks at 632 and 630 nm, respectively. Their UV-spectra showed the strong ³MLCT transition due to the strong coupling between the 5d orbital of the iridium center and the highest occupied molecular orbitals (HOMOs) of the ligands. The organic light emitting devices employing these compounds as the dopant were prepared and their electroluminescence was investigated. Both of the complexes exhibited the phosphorescence close to the saturated red emission at the CIE coordinate of x = 0.68, y = 0.31.     

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。     

Solution processable organic electro-phosphorescent iridium complex based on a benzothiazole derivative

We have synthesized a new solution processable iridium complex, di[2-(4′-octyloxyphenyl) benzothiazole]iridium(III)acetoacetone, [(OPBT)₂Ir(acac)], based on benzothiazole derivative for organic electro-phosphorescent devices. The synthesized molecule was identified by ¹H NMR and ¹³C NMR, and readily soluble in common organic solvents such as chlorobenzene. The UV–visible absorption and photoluminescence properties of pristine [(OPBT)₂Ir(acac) thin film as well as poly(N-vinylcarbzole) (PVK) thin film doped with the iridium complex were studied. The maximum UV–visible absorption and photoluminescence (PL) spectra are found to be at 337 nm and 547 nm, respectively. We have fabricated phosphorescent organic light-emitting devices using the ITO/PEDOT:PSS (40 nm)/PVK:(OPBT)₂Ir(acac) (40 nm)/Balq (40 nm)/LiF (1 nm)/Al (80 nm) configuration with the iridium complex as a triplet emissive dopant in poly(N-vinylcarbazole) (PVK) host. The electroluminescence (EL) devices showed greenish yellow light emission with maximum peak at 551 nm. Especially, the maximum external quantum and current efficiency of 1 mol% doped device were 1.74% and 4.89 cd/A, respectively.     

Broad band and white phosphorescent polymer light-emitting diodes in multilayer structure

Efficient phosphorescent polymer light-emitting diode with poly(vinylcarbazole) (PVK) doped by two or three iridium complexes in single and bilayer structures are studied. With (tris-(2-4(4-toltyl) phenylpyridine) (Ir(mppy)₃) as the green emitter and (1-phenylisoquinoline) (acetylacetonate) iridium(III) (Ir(piq)₂) as the red emitter the efficiency is as high as 23 cd/A with broad band emission from 500 nm to 720 nm. For white emission a second layer is added with blue emitter ((III) bis[(4,-6-di-fluorophenyl-pyridinato)N,C²] picolinate) (FIrpic) doped in PVK. White light containing three spectral peaks results with efficiency 8.1 cd/A. As the second blue layer is replaced by the fluorescent (poly(9,9-dioctylfluorene)) (PFO) white emission with high color rendering index 86 is achieved. The efficiency is 5.7 cd/A with peak luminance 8900 cd/m². For a given iridium complexes ratio the relative intensity of the green and red emission depends sensitively on the second blue layer.     

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.     

Efficient electrophosphorescence based on 2-(9,9-diethylfluoren-2-yl)-5-trifluoromethylpyridine iridium complexes

A novel cyclometalated ligand 2-(9,9-diethylfluoren-2-yl)-5-trifluoromethyl-pyridine (fl-5CF₃-py), and its complexes bis[2-(9,9-diethylfluoren-2-yl)-5-trifluoromethyl-pyridinto-C³, N]iridium (acetylacetonate) (fl-5CF₃-py)₂Ir(acac) (5) and bis[2-(9,9-diethylfluoren-2-yl)-5-trifluoromethylpyridinto-C³, N] iridium (2-picolinic acid) (fl-5CF₃-py)₂Ir(pic) (6) were synthesized, respectively. Trifluoromethyl group and 2-picolinic acid were incorporated into iridium ligands to tune luminescent color. Emission spectra of 5 and 6 in THF solutions were 589 and 572 nm. Decomposition temperatures (Td) of 5 and 6 were 326 and 360 °C. Multilayer electrophosphorescent devices were fabricated using 5 and 6 as emitter dopants with electroluminescent spectra maximized at around 585 and 571 nm, respectively. The relatively high efficiencies of the devices and their slow rate of decay against increases in current densities indicated that (fl-5CF₃-py)₂Ir(acac) or (fl-5CF₃-py)₂Ir(pic) was a promising emitter for practical device applications.     

Synthesis and luminescence of red,fluorinated iridium (III) complexes containing alkenyl benzothiazole ligand

Two novel iridium(III) complexes (2-FSBT)₂Ir(acac) and (4-FSBT)₂Ir(acac) (2-FSBT, (E)-2-(2-fluorostyryl)benzo[d]thiazole; 4-FSBT, (E)-2-(4-fluorostyryl)benzo[d]thiazole; acac, acetylacetone) were synthesized and characterized by ¹H NMR and mass spectrometry. The organic light emitting diodes based on these complexes with the structure of ITO/m-MTDATA(10 nm)/NPB(20 nm)/CBP:Ir-complex(X %, 30 nm)/BCP(10 nm)/Alq₃(30 nm)/LiF(1 nm)/Al(100 nm) were fabricated. The device based on (2-FSBT)₂Ir(acac) exhibited a maximum efficiency of 9.32 cd/A, a luminance of 8800 cd/cm²; and the device based on (4-FSBT)₂Ir(acac) showed a maximum efficiency of 8.5 cd/A, a luminance of 6986 cd/cm². The Commission International de L’Eclairage (CIE) coordinates (1931) of these complexes were (0.619, 0.381) and (0.621, 0.378), respectively.