新型三线态喹喔啉铱(Ⅲ)配合物的微波合成及其光致发光

在微波辅助加热下,4,4'-二氟-2,3-二苯基喹喔啉(DPQF)与水合三氯化铱(IrCl3·H2O)反应,合成了一种新型三环喹喔啉铱配合物[Ir(DPQF)3],通过1HNMR、元素分析和质谱方法对配合物结构进行了表征,并研究了配合物的吸收光谱和光致发光光谱.结果表明,配合物Ir(DPQF),在391和453 nm处...     

一种绿色铱磷光配合物的合成及性能研究

以3-苯基苯硼酸、2-溴吡啶为原料,通过与三氯化铱的配合反应,合成了一种绿色有机电致磷光材料[二(2-联苯基吡啶)](2-吡啶甲酸)合铱(Ir(bppy)2pic),通过1H NMR、质谱对其进行了结构表征。并对配合物的紫外吸收和发光性能进行考察,研究表明其在405 nm和475 nm处存在单重态1MLCT和三重态3MLCT的吸收峰;最大发射波长为503 nm,是一种具有更加饱和的发射光谱的绿色磷光材料。     

一种铱磷光配合物的合成表征及性能研究

利用2-苯基吡啶(ppy)、三水合氯化铱(IrCl_3·3H_2O)和2-吡啶甲酸(pic)配位,得到铱配位物Ir(ppy)_2pic,合成产率9 0%,该方法适合于Ir(ppy)2pic的批量制备。通过元素分析、核磁共振(~1H-NMR、~(13)C-NMR)和质谱(MS)对产物分子结构进行了表征,此外结合紫外吸收光谱(UV-Vis)和荧光光谱(PL)对其光物理性能进行了研究。结果表明:该配合物在紫外谱图上的250~300 nm处出现了强的配体单重态π-π*自旋跃迁吸收峰,在400~500 nm处出现了铱(Ш)到配体的单重态和三重态(~1MLCT和~3MLCT)电子跃迁吸收峰,在荧光光谱的514 nm处有较强的金属配合物三重态的磷光发射峰,显示为一种高效的绿色磷光材料。     

新型红色磷光铱（Ⅲ）配合物的合成及表征

以2-（2’-苯并噻吩基）吡啶（btp）、对乙烯基苯甲酸（VBA）为原料,通过与水合三氯化铱（IrCl3·3H2O）配合,得到了一种新型铱（Ⅲ）配合物Ir（btp）2（VBA）,通过元素分析、FT—IR光谱及^1HNMR谱对其进行了结构表征,并研究了其UV—Vis吸收光谱和光致发光光谱。结果表明,配合物在403和462nm处存在单重态和三重态的吸收峰,在630nm处有较强的金属配合物三重态的磷光发射峰,是一种新型红色磷光材料。     

高效绿色磷光铱配合物的合成与发光性能

设计、合成了一个新颖的环金属配体1-（4-甲氧基-苯甲基）-2-（4-甲氧基苯基）-苯并咪唑（MBMPB）,并以乙酰丙酮（Hacac）为辅助配体合成了高效绿色铱配合物Ir（MBMPB）2（acac）。通过1H NMR和元素分析对其进行结构表征,且详细研究了其光物理性质。结果表明,配合物在402 nm和446 nm处存在1MLCT和3MLCT的吸收带,在492 nm处有较强的绿光发射,同时具有高的光致发光效率和短的激发态寿命。     

一种基于苯基噌啉类铱配合物的新型汞离子探针

以3,4-二苯基噌啉为环金属配体,6,7-二氰基二吡啶并喹喔啉为解离配体合成了一种新型环金属铱配合物.配合物的结构通过红外、质谱、核磁进行了表征.配合物的最大发射波长为603 nm,磷光寿命为1.17 μs.在与金属阳离子的作用中,该配合物表现出了对Hg2+的选择性磷光淬灭性能,能作为Hg2+的磷光探针.     

两种新型磷光金属铱配合物的合成及光电性能研究

以3-甲基-1-(2-氟苯基)咪唑和3-甲基-1-(4-氟苯基)咪唑作为第一配体,2-甲酸吡啶作为第二配体,合成了以铱(III)为内核的两种有机电致磷光材料(o-fpmi)2Ir(pic)(o-fpmi=3-甲基-1-(2-氟苯基)咪唑,pic=2-甲酸吡啶)和(fpmi)2Ir(pic)(fpmi=3-甲基-1-(4-氟苯基)咪唑)。通过核磁1H NMR和液相质谱LC-MS对其结构进行分析确认,并用紫外-可见吸收光谱、荧光发射光谱和循环伏安法测定其光电物理性能,热重分析测定铱配合物的热稳定性。结果表明,(fpmi)2Ir(pic)和(o-fpmi)2Ir(pic)的紫外吸收峰值为231,270,300,360 nm和237,281,315,370 nm,最大荧光发射波长为502 nm和508 nm,主要来源于三重态3MLCT的辐射跃迁,热分解温度为300℃,是一类热稳定性好的蓝绿色发光材料。     

新型黄光铱磷光配合物的合成、表征及性能研究

通过在2,4-二氯吡啶上引入3-联苯基,合成了一种以2,4-二(3-联苯)吡啶为主配体,以2,2,6,6-四甲基-3,5-庚二酮为辅助配体的新型有机电致磷光材料,通过元素分析、红外光谱、~1H NMR和质谱对产物进行了结构表征,利用X射线单晶衍射仪测定了配合物的晶体结构。并对其用紫外-可见吸收、光致发光、热稳定性等进行研究。研究表明,配合物在395和465nm处存在单重态~1MLCT(金属到配体的电荷跃迁)和三重态~3MLCT的吸收峰;其初始分解温度为405℃(对应于10%质量损失),最大发射波长为570nm,是一种可用于白色有机电致发光器件的新型黄色发光磷光材料。     

铱配合物磷光探针的合成及细胞荧光成像

磷光铱配合物具有良好的光热稳定性、发光颜色可调性、较长的激发寿命和较高的发光效率等特点。以2-苯基并噻唑衍生物(含有醛基、乙氧基和叔丁基)为主配体、1,10-邻菲罗啉为辅助配体,合成3个磷光铱配合物。通过核磁共振谱和高分辨质谱对其结构进行表征,利用荧光光谱和紫外-可见吸收光谱对其发光性能进行研究,并测试了磷光铱配合物的细胞荧光成像作用。     

新型砜基喹喔啉衍生物的合成和体外抗肿瘤活性研究

合成了新型的砜基喹喔啉衍生物并对其体外抗肿瘤活性进行初步评价。采用Kinase-Glo Luminescent Assay,Lance Ultra Assay,SRB法测试砜基喹喔啉类衍生物的体外抗肿瘤活性。9个砜基喹喔啉衍生物经NMR,MS表征;砜基喹喔啉衍生物对PI3Kα、哺乳动物雷帕霉素靶蛋白(mTOR)均无明显的抑制作用;其中,化合物3-(3-氨基苯磺酰基)-N-(3,5-二甲氧基苯基)喹喔啉-2-胺(12),N-(3-(3-(3,5-二甲氧基苯胺基)喹喔啉-2-基砜基)苯基)乙酰胺(13)、1-(3-(3-(3,5-二甲氧基苯胺基)喹喔啉-2-基砜基)苯基)-3-乙基脲(15)和N-(3-(3-(3,5-二甲氧基苯胺基)喹喔啉-2-基砜基)苯基)吗啉-4-甲酰胺(16)对PC3细胞的增殖抑制活性(IC₅₀)均<3μmol/L。砜基喹喔啉类衍生物具有中等强度的抗肿瘤活性。     

橙红色磷光铱(Ⅲ)配合物的合成及表征

以二苯基吡啶(ppy)和2,2'-联吡啶-4,4'-二羧酸(H2dcppy)为配体,与水合三氯化铱(IrCl3·3H2O)配位,我们合成了一种结构新颖的具有橙红色磷光发射的金属铱配合物Ir(PPY)2(H2dcppy)PF6,其结构通过FT-IR光谱和核磁共振氢谱得到了确认.紫外吸收光谱和荧光光谱表明,该配合物具有明显...     

2-巯基吡啶与Cu(I)配合物的合成、晶体结构及光物理性质

利用Cu(I)前体[Cu(CH3CN)4]BF4与配体2-巯基吡啶、邻菲罗啉进行反应,合成了一种新型铜(I)配合物:{[Cu3(py2tH)6](BF4)3.H2O}n。运用X-射线单晶衍射方法确定了其晶体结构。同时,利用现代波谱方法对配合物的光物理性质进行研究。发射光谱显示在632nm处的发射峰属于金属到配体的电荷跃迁,即MLCT。     

Ru(II) and Zn(II) complexes of multicomponent ligands incorporating triazine-based tridentate ligands

Ru(II) and Zn(II) complexes of multicomponent ligands have been synthesised and characterised incorporating triazine-based coordinating motifs with pendant phenanthryl and phenyl–phenanthryl groups. At room temperature the ligands emit from intra-ligand charge-transfer (ILCT) states, the energy of which may be lowered significantly by metal–ion coordination (e.g. Zn(II)). The ILCT state is efficiently quenched in the Ru(II) complexes by energy transfer to a low-lying metal–ligand charge-transfer ³MLCT state.     

新型钌多联吡啶配合物的合成及其对Hg^2＋的选择性“肉眼”识别

将二唑引入联吡啶,合成了配体4,4′-二[2-（4-壬氧基苯基）-5-苯基-1,3,4-二唑基]-2,2′-二联吡啶（DPOD）,经多步配位反应与RuCl3.3H2O反应制备相应的钌配合物Ru（DPOD）2（NCS）2,并通过红外光谱（IR）、紫外可见吸收光谱（UV-Vis）和元素分析对其进行了表征。对Hg^2＋、Zn^2＋、Pb^2＋、Co^2＋等金属离子的滴定实验表明,仅在Hg^2＋作用下,该配合物的MLCT态吸收由580 nm蓝移至566 nm,肉眼即可识别其溶液由墨蓝色变为粉红色。该配合物是一种较好的比色汞离子探针。     

Photoconductivity and photovoltaic effect of charge-transfer complex of poly[4-phenyl-2,6-(p-phenoxy) quinoline] and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

A new polymer containing a heterocyclic quinoline unit in the main chain, poly[4-phenyl-2,6-(p-phenoxy) quinoline] (PQ), was synthesized by an acid-catalyzed self-condensation reaction. We have found that PQ, which is generally a good insulator itself, can show photoconductivity when doped with an electron acceptor. From the UV-VIS absorption spectra, we found that PQ can form a charge-transfer (CT) complex with an electron acceptor, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The CT complex of the PQ-DDQ mixture showed distinct photoconductivity. Employing the DDQ composition ranging from 5 to 10 wt %, the ratio of dark and photoconductivity was calculated to be about 1 : 100 at an applied electric field of 10₅ V/cm. Additionally, the bilayer sample of PQ/DDQ exhibited a significant photovoltaic effect. The photovoltaic current increased with increasing photointensity. The open-circuit voltage was measured ranging from 0.4 to 0.7 V and the photovoltaic conversion efficiency was calculated to be 10^?3?10_?2%. The PQ film treated with DDQ vapor showed a relatively higher photovoltaic effect than that of the sample treated with DDQ solution. © 1993 John Wiley & Sons, Inc.     

NIR-Absorbing RuII Complexes Containing α-Oligothiophenes for Applications in Photodynamic Therapy

The design of near-infrared (NIR)-active photosensitizers (PSs) for light-based cancer treatments such as photodynamic therapy (PDT) has been a challenge. While several NIR-Ru^II scaffolds have been reported, this approach has not been proven in cells. This is the first report of NIR-Ru^II PSs that are phototoxic to cancer cells, including highly pigmented B16F10 melanoma cells. The PS family incorporated a bis(1,8-naphthyridine)-based ligand (tpbn), a bidentate thiophene-based ligand (nT; n=0–4), and a monodentate 4-picoline ligand (4-pic). All compounds absorbed light >800 nm with maxima near 730 nm. Transient absorption (TA) measurements indicated that n=4 thiophene rings ( 4T ) positioned the PDT-active triplet intraligand charge transfer (³ILCT) excited state in energetic proximity to the lowest-lying triplet metal-to-ligand charge transfer (³MLCT). 4T had low-micromolar phototoxicity with PI_vis and PI_733nm values as large as 90 and 12, respectively. Spectroscopic studies suggested that the longer-lived (τ_TA=3–6 μs) ³ILCT state was accessible from the ³MLCT state, but energetically uphill in the overall photophysics. The study highlights that phototoxic effects can be achieved with NIR-absorbing Ru^II PSs as long as the reactive ³ILCT states are energetically accessible from the low-energy ³MLCT states. It also demonstrates that tissue-penetrating NIR light can be used to activate the PSs in highly pigmented cells where melanin attenuates shorter wavelengths of light.     

Photochemistry of trichloro(phenylazo)bis(triphenylphosphine)ruthenium(II) induced by Ru to phenyldiazonium MLCT excitation

The complex trichloro(phenylazo)bis(triphenylphosphine)ruthenium(II) shows a longest-wavelength absorption at λ_max = 520 nm which is assigned to a Ru(II) → phenyldiazonium⁺ MLCT transition. MLCT excitation leads to the oxidation of the metal and reduction of the diazonium cation which decays to nitrogen and phenyl radical.