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。     

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。     

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。     

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。     

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。     

一种新型三氮唑铱(Ⅲ)配合物的合成和表征

以5-(4-氟苯基)-1,3-二甲基-1H-1,2,4-三唑(fdpt)为环金属配体、乙酰丙酮(Hacac)为辅助配体合成出一种新型铱(Ⅲ)配合物Ir(fdpt)2(acac)。采用元素分析、红外光谱、核磁共振谱分析和单晶X衍射对其组成和化学结构进行了表征。结果表明,该配合物化学组成为C25H25F2IrN6O2,属于单斜晶系,P21/c空间群。晶胞参数为a=1.58917(14) nm,b=1.64798(15) nm,c=1.06146(9) nm,β=94.741(3)°,V=2.7704(4) nm³,Z=4。     

氨基酸类铱(Ⅲ)配合物的合成、表征及对汞离子的识别

以4-(苯并[d]噻唑-2-基)-N,N-二甲基苯胺(1)、L-丝氨酸作为主配体和辅助配体,合成了一种新型环金属铱配合物(2),所有化合物的结构通过¹H NMR、MS和IR进行了表征确认。通过紫外吸收光谱和荧光发射光谱研究了铱配合物(2)的光物理性质,并采用含时密度泛函理论(TDDFT)对其最低能量电子跃迁和最低三重激发态进行了计算。而且铱配合物(2)的荧光发射光谱可选择性地被汞离子猝灭,暗示着此配合物可作为一种高效的turn-off型汞离子磷光传感器。     

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。     

Multicolor emitting from a single component emitter: New iridium(III) complexes with ancillary ligand 2-(2-hydroxyphenyl) benzothiazole

Four new types of Ir(III) complexes (ppy)₂Ir(LX) (ppy = 2-phenylpyridine, LX = BTZ, 3-MeBTZ, 4-MeBTZ, and 4-TfmBTZ) were synthesized and investigated by optical spectroscopy, electrochemistry as well as density functional theory (DFT). These complexes all exhibit multi-emission bands under ultraviolet light excitation at room temperature because there are efficient energy transfers between different excited states (¹LC, ¹MLCT, ¹ILCT, ³MLCT, ³ILCT), especially for complexes I–III. The blue emitting relates to the fluorescence of Ir(R-BTZ) and the green emission originates in ³MLCT emission of Ir(ppy)₂ fragment. The red emission corresponds to ³ILCT transition (R-BTZ → ppy) for complexes I–III, but ³MLCT transition of Ir(4-TfmBTZ)₂ fragment for (ppy)₂Ir(4-TfmBTZ). The red emission peak wavelength can be fine-tuned from 583 to 626 nm by the electron withdrawing or donating substituent at 3- or 4-position of BTZ ligand. For these single component complexes with multicolor emitting, a very promising application is the generation of white light. Although these complexes span non-uniformly the spectral range of the visible region and consequently are insufficient to produce satisfactory white light characteristics, the luminescence mechanism of them provides a new strategy for designing organic white light-emitting material.     

双(二甲氧基苯基膦)二氯化钯(Ⅱ)的合成及化学结构表征

以氯亚钯酸钠、双甲氧基苯基膦酸盐为起始原料,通过配位取代反应合成了大配体C-C偶联催化剂双(二甲氧基苯基磷)二氯化钯(Ⅱ)(Pd Cl2[P(OMe)2Ph]2)。优化的一步合成条件为:在氩气保护下,向双甲氧基苯基膦酸盐的四氢呋喃溶液中滴加0.5倍摩尔分数的氯亚钯酸钠水溶液,50℃反应得到配合物,产率为96.5%。采用核磁共振(1H NMR)及单晶X射线衍射(XRD)对产物化学结构进行测定和解析。1H NMR显示,2个苯环及4个甲氧基上的氢核信号的化学位移、峰面积与目标化合物对应一致;单晶XRD确定其晶体为单斜晶系空间群为C2/c,获得了相应的键长和键角参数。     

(1,5-环辛二烯)氯化钌(II)多聚体的合成及表征

在无水乙醇介质中,将水合三氯化钌与1,5-环辛二烯加热回流,一步合成了(1,5-环辛二烯)氯化钌(II)多聚体[Ru(cod)Cl2]n,产率96%。用元素分析、核磁共振(¹H-NMR、¹³C-NMR)和红外光谱(IR)等分析表明产物为目标化合物。     

蓝光材料FIrpic的合成、结构表征及光物理性能测试

以水合三氯化铱和 dfppy 为原料,在乙二醇单乙醚溶剂中反应得氯桥二聚体(dfppy)2Ir(μ-Cl2)Ir(dfppy)2,然后在碱性条件下与2-吡啶甲酸反应合成出 FIrpic。通过核磁共振谱(1HNMR、13CNMR)、质谱、红外光谱和单晶X射线衍射等确定了分子结构,高效液相色谱法(HPLC)测试了纯度,利用紫外-可见吸收光谱和光致发光光谱对其光物理性能进行了测试。结果表明：FIrpic为电中性八面体配合物,在476 nm处出现了较强的蓝光发射,其合成产率大于90%,纯度为99.22%,该方法适于FIrpic的批量制备。     

Theoretical studies on electronic structures,spectra and charge transporting properties of a series of Pt(CN)2 complexes

We report a quantum-chemical study of electronic, optical and charge transporting properties of four platinum (II) complexes, Pt(C^ΛN)₂ (C^ΛN = phenylpyridine or thiophenepyridine). The lowest-lying absorptions at 442, 440, 447 and 429 nm are all attributed to the mixed transition characters of metal-to-ligand charge transfer (MLCT) and ligand-centered (LC) π → π* transition. While, unexpectedly, the lowest-lying phosphorescent emissions at 663, 660, 675 and 742 nm are mainly from metal-to-ligand charge transfer (³MLCT) ligand-centered (LC) π → π* transition. Ionization potential (IP), electron affinities (EA) and reorganization energy (λ_{hole/electron}) were obtained to evaluate the charge transfer and balance properties between hole and electron. The calculated results reveal that the small structure changes of the charged states relative to the neutral ones, and the smaller IP and EA values indicate that they exhibit a relatively high structural stability versus the injection of one charge and have better holes than electron-injection abilities. The smaller λ values and the smaller differences (within 0.06 eV) between λ_hole and λ_electron indicate the better transfer balance between holes and electrons. Moreover, the attached methyl groups slightly improve the hole-injection ability and deduce the electron-injection ability. The strong phosphorescence emission and the favorable transporting properties compared with other reported complexes indicate their potential applications in as emitters OLEDs.     

A new conducting polymer of 2,5-bis(2-thienyl)-1H-(pyrrole) (SNS) containing carbazole subunit: Electrochemical, optical and electrochromic properties

We report here the synthesis of a new electroactive monomer 3,6-di-tert-butyl-[4-(2,5-di-2-thienyl-1H-pyrrol-1-yl)phenyl]-9H-carbazole in five steps and polymerization of this monomer by two different procceses: Kumada Coupling and electro-oxidative. The product obtained by chemical polymerization exhibits a high thermal stability and narrow molecular weight distribution. While, in the UV–vis absorption spectrum of monomer the absorption peaks appear at 338 nm, the chemically synthesized polymer absorbs at 428 nm with 90 nm red shift. Cyclic voltammogram of monomer shows two separate oxidation processes which reflect the first oxidation at +0.84 V and a second one at +1.43 V. When the polymeric film prepared by electrochemical process was subjected to a repeated cyclic scan between −0.2 V and +1.0 V, it switches among three different colors (orange, green and blue). The oxidation and reduction response times were calculated as 2.0 s for this polymer film and exhibits high redox stability. The results anticipate that this kind of polymers can be used for designing electrochromics based on the use of one molecule for the generation of three basic colors (RGB).     

Synthesis,photo- and electroluminescent properties of norbornene based platinum-containing copolymers

Norbornene based monomers containing the 2-phenylpyridinato–N,C²′ platinum(II) complex bonded by acetylacetonate or pyrazolonate anchor groups were synthesized and copolymerized with a carbazole-containing norbornene comonomer by ring-opening metathesis polymerization (ROMP). The photo- and electroluminescence spectra of the resulting Pt-copolymers are similar. They consist of broad bands with maxima at 495, 530 and 565 nm which arise from the mixed ligand centered (LC) and metal to ligand charge transfer (MLCT) transitions. The copolymer with the cyclometalated platinum(II) complex bonded to the polymer chain via the pyrazolonate anchor group revealed the highest brightness of electroluminescence (260 cd/m² at 21 V).