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。     

一种联吡啶类铱配合物的合成及光物理性能测试

以2-(2,4-二氟苯基)吡啶为主配体,2,2''-联吡啶为辅助配体,设计合成出了一种联吡啶铱配合物[Ir(dfppy)2(bpy)]PF6 (dfppy = 2-(2,4-二氟苯基)吡啶,bpy = 2,2''-联吡啶)。通过元素分析、质谱、核磁共振谱、红外光谱和X射线单晶测试表征了配合物的化学结构,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。结果表明,配合物的最大发射波长为515 nm,发光颜色为绿光。     

Mesoporous silica doped with a chemosensor based on phosphorescent copper(I) complex: Synthesis,characterization, photophysical property,and sensing behavior towards molecular oxygen

In this paper, we report the synthesis, crystal structure, photophysical properties, and electronic nature of a phosphorescent Cu(I) complex of [Cu(OP)(PPh₃)₂]BF₄, where OP and PPh₃ stand for 2-(5-phenyl-[1,3,4]oxadiazol-2-yl)-pyridine and triphenylphosphine, respectively. [Cu(OP)(PPh₃)₂]BF₄ is a yellow-emitting complex with a phosphorescence peaking at 552 nm and a long excited state lifetime of 83.5 μs under N₂ atmosphere. Density functional calculation reveals that the emission comes from a triplet metal-to-ligand-charge-transfer excited state. We dope [Cu(OP)(PPh₃)₂]BF₄ into a mesoporous silica matrix of MCM-41, hoping to explore the possibility of using the doped silica as an oxygen sensing material. The resulted samples exhibit a maximum sensitivity of 4.48 towards oxygen with short response time due to the large surface-area-to-volume ratio of MCM-41 matrix, and no photobleaching is detected in these samples.     

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...     

A phosphorescent copper(I) complex: Synthesis,characterization, photophysical property,and sensing performance towards molecular oxygen

In this paper, we report the synthesis, crystal structure, photophysical properties, and electronic nature of a phosphorescent Cu(I) complex of [Cu(PYB)(POP)]BF₄, where PYB and POP stand for 2-pyridin-2-yl-1H-benzoimidazole and bis(2-(diphenylphosphanyl)phenyl) ether, respectively. [Cu(PYB)(POP)]BF₄ renders yellow phosphorescence peaking at 561 nm, with a long excited state lifetime of 13.4 μs. Density functional calculation reveals that the emission comes from a triplet metal-to-ligand-charge-transfer excited state. We electrospun composite nanofibers of [Cu(PYB)(POP)]BF₄ and polystyrene, hoping to explore the possibility of using the composite nanofibers as an oxygen sensing material. The finally obtained samples with average diameter of ～900 nm exhibit a maximum sensitivity of 4.20 towards molecular oxygen with short response/recovery time (8 s/16 s) due to the large surface-area-to-volume ratio of nanofibrous membranes. No photobleaching is detected in these samples.     

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。     

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.     

Diamine ligands with multiple coplanar conjugation rings and their phosphorescent copper complexes: Synthesis,characterization, crystal structures,and photophysical property

In this paper, we report a series of diamine ligands with multiple coplanar conjugation rings and their corresponding phosphorescent Cu(I) complexes, including their synthesis, crystal structures, photophysical properties, and electronic nature. Geometric parameters suggest that the Cu(I) center localizes at a distorted tetrahedral geometry within the Cu(I) complexes. Theoretical calculation reveals that all emissions originate from triplet metal-to-ligand-charge-transfer excited state. It is found that the free rotation of conjugation rings may compromise the coplanar plane and thus has little effect on the photophysical property of their corresponding Cu(I) complexes. But excess coplanar conjugation moiety is harmful for emissive state. The detailed quenching mechanism is investigated.     

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0.50μs和0.63μs。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。     

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。     

Synthesis, characterization, and electroluminescent properties of iridium complex containing 4-phenybenzoquinoline ligand

A phosphorescent iridium(III) complex Ir(PBQ)₂(acac) (PBQ: 4-phenylbenzoquinoline, acac: acetylacetone) was designed and synthesized, and the single crystal of this complex was obtained. This complex shows well optoelectronic properties. The organic light emitting devices (OLEDs) based on this complex were successfully fabricated with the device configuration of ITO/NPB or TCTA (40 nm)/Ir-complex: CBP (7%, 30 nm)/BCP (15 nm)/Alq (30 nm)/LiF (1 nm)/Al (100 nm). Using TCTA as the hole-transporting material, the device gives an extremely high external quantum efficiency of 14.6% at 5.0 V, a brightness of 61,693 cd/m² at 16.0 V, and a power efficiency of 37.0 lm/W at 3.5 V.     

Low driving voltage and efficient orange-red phosphorescent organic light-emitting devices based on a benzotriazole iridium complex

Efficient orange-red phosphorescent organic light-emitting devices (PHOLED) with various doping concentrations of benzotriazole–iridium complex [(TBT)₂Ir(acac)] (bis[4-(2H-benzotriazol-2-yl)-N,N-diphenyl-aniline-N¹,C³] iridium acetylacetonate) in 4,4′-N,N′-di(carbazolyl) biphenyl (CBP) host were fabricated. The sterically hindered iridium ligands alleviate self-quenching of the phosphorescence at high doping levels. Under the optimal doping concentration of 20 wt.%, the maximum external quantum efficiency (EQE), luminance and power yield reach 9.06%, 15.81 cd/A and 13.8 lm/W, respectively. Increasing the doping concentration from 5% to 30 wt.% significantly decreases the driving voltage. The driving voltage of 30% (TBT)₂Ir(acac) doped device is only 3.16 V at 1 mA/cm² with power yield of 13.32 lm/W.     

Oxygen sensing nanofibers doped with red-emitting Eu(III) complex: Synthesis,characterization, mechanism,and sensing performance

In this paper, we synthesize a novel diamine ligand of PIP and its corresponding Eu(III) complex of Eu(DBM)₃PIP, where PIP = 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline, and DBM = 1,3-diphenyl-propane-1,3-dione. The UV–Vis absorption spectra, low temperature phosphorescence spectra, energy transfer mechanism, excited state lifetime of Eu(DBM)₃PIP, as well as its photoluminescence spectra, are investigated in detail. Data suggest that the emission of Eu(DBM)₃PIP is quenchable by molecular oxygen due to the back-energy transfer process. By doping Eu(DBM)₃PIP into a polymer matrix of poly(vinylpyrrolidone) (PVP), the oxygen sensing performance of the resulted nanofibrous membrane is investigated. Finally, the 0.6 wt% doped sample exhibits a linear response towards molecular oxygen, with a sensitivity of 3.5 and response/recovery time of 15 s/24 s.     

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。     

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。     

Synthesis,photophysical and electrophosphorescent properties of a novel fluorinated rhenium(I) complex

A novel fluorinated rhenium complex, i.e., Re-BFPP (BFPP, 2, 3-bis(4-fluorophenyl)pyrazino[2,3-f][1,10]phenanthroline) was designed, synthesized and characterized by ¹H NMR and mass spectroscopy. The light-emitting and electrochemical properties of this complex were studied. The organic light-emitting diodes (OLEDs) employing Re-BFPP as a dopant emitter with the structures of ITO/m-MTDATA (10 nm)/NPB (20 nm)/CBP: X wt.% Re-BFPP (30 nm)/Bphen (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al (100 nm) were successfully fabricated and a broad electroluminescent peak at 553 nm was observed. The 10 wt.% Re-BFPP doped device exhibited the maximum luminance of 6342 cd/m² and a peak current efficiency of 17.9 cd/A, corresponding to the power efficiency of 8.1 lm/W.     

A series of water soluble RE(III) complexes: Synthesis,characterization, photophysical property and sensing activity towards Cr(III)

In this paper, four water soluble rare-earth(III) fluorescent chemosensors, Na₃RE(PDA)₃ (PDA = pyridine-2,6-dicarboxylic acid, and RE = Sm, Eu, Tb, Dy), are synthesized and characterized. Their excitation and emission spectra, fluorescence responses towards Cr(III), quenching mechanism, oxygen and thermal sensitivity of the complexes are systemically studied. The emission intensity and the excited state lifetimes of the four complexes decrease with increasing concentration of trivalent chromium (Cr(III)). Their sensing behavior towards Cr(III) is investigated by fluorescence spectroscopy. Results suggest that Na₃Dy(PDA)₃ exhibits highest sensitivity and linear spectral response towards Cr(III) (Stern–Volmer constant = 0.461 × 10⁷ L/mol, linearity = 0.996). It is note worthy that oxygen has little effect on the emission of Na₃RE(PDA)₃ complexes. These important advantages make themselves promising candidates to be utilized in actual applications.     

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2.40μs。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。     

原位自生SiC纳米线掺杂SiOC陶瓷粉体的制备与介电性能

以二茂铁为催化剂,催化裂解陶瓷聚合物先驱体制备了原位自生SiC纳米线掺杂的SiOC陶瓷粉体。SiC纳米线为堆垛方向为<111>的β相单晶体,直径为10-100nm,长度可达数微米,均匀分布在SiOC粉体中。基于SiC纳米线微观结构分析,探讨了纳米线的生长机制。研究了复合陶瓷粉体的介电性能,结果发现,SiC纳米线含量可调控复合粉体的电性能,较高含量纳米线可赋予复合粉体较高的介电实部与虚部。