双(二叔丁基苯基膦)二卤化Pt(Ⅱ)配合物的合成及结构测试

采用铂替代钯合成了以二叔丁基苯基膦[(t-Bu)_2PPh]和卤素(Cl、Br)为配体的Pt(Ⅱ)配合物。以氯化铂(PtCl_2)和溴化铂(PtBr_2)为起始原料,二甲亚砜(DMSO)为溶剂,在氮气保护下与二叔丁基苯基膦反应,得到目标化合物。结果表明,Pt[(t-Bu)_2PPh]_2Cl_2产率为96.9%,Pt[(t-Bu)_2PPh]_2Br_2产率为94.1%,2种化合物的纯度均大于99%。通过元素分析、核磁共振(~1H-NMR)分析和单晶X射线衍射(XRD)分析测定了目标化合物的化学结构,结果显示,配合物均为trans-四配位的平面正方形配合物,Pt(Ⅱ)处于配位平面的中心,分别与2个Cl或者Br和P键合,形成4配位的平面四边形的结构,2个卤素原子和膦配体处于反位。     

[2,2'-双(二苯基膦)-1,1'-联萘]二氯化钯的合成及其结构表征

以氯亚钯酸钠为钯源与Binap反应,合成了[2,2'-双(二苯基膦)-1,1'-联萘]二氯化钯,收率达97.4%,合成原料相对廉价易得,合成过程简单、绿色环保。通过元素分析、红外光谱(IR)以及核磁共振分析(1H-NMR、31P-NMR)等手段,证实了所合成产物的组成与结构,产物具有较高纯度。     

有机膦配体对钯分子偶联催化剂活性的影响

采用3种不同的有机膦配体,设计和合成出3个有机膦钯(II)配合物,测试和表征了它们的化学结构,分别为trans-{Pd[(t-Bu)2PPh]2Cl2}、trans-[Pd(Amphos)2Cl2]、cis-[Pd(Xantphos)Cl2] ((t-Bu)2PPh=二叔丁基苯基膦、Amphos=二叔丁基-(4-二甲基氨基苯基)膦、Xantphos=4,5-双二苯基膦-9,9-二甲基氧杂蒽)。在2个Suzuki和1个Sonogashira偶联反应模型上,测定了它们的催化活性,考察了膦配体对钯分子偶联催化剂活性的影响,发现膦配体对催化活性有重要影响,且对应不同的反应模型其影响程度不同,影响机制与膦配体的配位能力和分子的空间体积有关。     

冠状四核钯(Ⅱ)配合物的合成和晶体结构

合成了一种用作前驱体的、中性、具有冠状结构的新型水溶性四核钯配合物十一水·醋酸亚胺合钯([CH_3COO)_4Pd_4(NH_2)_4]·11H_2O),用元素分析和X射线单晶衍射仪(XRD)对其结构进行了表征,用热重-差热(TG-TDA)测试其热分解特性。结果表明,该化合物为正交晶系、Pccn空间群,其晶体它的结构是以4个(CH_3COO)Pd片段分别和4个-NH_2配体桥接,形成八原子的环状四核钯的配合物,也获得了该配合物的键长和键角等参数。TG-DTA测试显示化合物分解峰出现在231.4℃(低分解温度),该配合物中不含氯、膦和硝酸根,可作为新型的钯前驱体。     

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。     

2-(2-喹啉偶氮)-1,3-二氨基苯光度法测定钯的研究

合成了新试剂2-(2-喹啉偶氮)-1,3-二氨基苯(QADAB),并研究了其与钯的显色反应,在0.2～3.0mol/LHClO4介质中,QADAB与钯反应生成2:1稳定络合物,体系λmax=590nm,ε=8.08×104L·mol-1·cm-1。钯含量在0.01～1.2mg/L内符合比尔定律。本方法用于一些含钯样品中钯含量的测定,结果令人满意。     

羧酸铑(II)轴向配合物的合成、表征及催化性能

以羧酸铑(II)为母体,吡啶-2-基(吡啶-4-基)甲酮(24ma)为轴向配体,合成了4种新型羧酸铑(Ⅱ)轴向配合物,且成功培养出化合物单晶。使用1H NMR、13C NMR、MS、IR和X-单晶射线衍射对其结构进行表征,讨论了取代基和轴向配体对分子结构的影响,并初步测试了它们对美罗培南类化合物合成反应的催化性能。结果表明,与母体分子羧酸铑(II)相比,所选定的羧酸铑(Ⅱ)轴向配合物因在反应体系中溶解度较差、配体不易解离等原因,导致催化合成美罗培南类化合物的产率不高。     

双(2,2,6,6-四甲基-3,5-庚二酮酸)钯(Ⅱ)的制备及成膜性能

以二氯化钯和2,2,6,6-四甲基-3,5-庚二酮为原料,在甲醇中合成了一种新的β二酮前驱体-双(2,2,6,6-四甲基-3,5-庚二酮酸)钯(Ⅱ)。通过元素分析、红外光谱、核磁共振氢谱及单晶X射线衍射等技术对合成的前驱体进行了结构表征。热重-差热分析表明,在N2气氛中,当温度升到291℃时,前驱体基本挥发完全。采用合成的前驱体通过金属有机化学气相沉积(MOCVD)技术在石英上沉积制备钯薄膜,利用XRD和AFM分析手段对薄膜的结构和表面形貌进行了表征。结果表明,所得到的薄膜纯净,无其他杂质存在,薄膜表面连续、致密。     

[Ir(ppy)2(dcbpy)]PF6的合成、表征及光物理性能研究

以氯桥二聚体(ppy)2Ir(μ-Cl2)Ir(ppy)2、4,4''-二羧基-2,2''-联吡啶和六氟磷酸铵为原料合成了一种阳离子型铱配合物[Ir(ppy)2(dcbpy)]PF6,产率94.9%。并通过元素分析、质谱、红外光谱以及核磁共振谱表征确认了目标产物的分子结构。以溶剂缓慢挥发法培养出配合物单晶,经X射线单晶衍射仪表征、计算,获得了晶体结构参数。紫外-可见吸收光谱和光致发光光谱的研究表明,该配合物常温最大发射位于582 nm处,显示发射强烈的黄光。     

系列金(I)有机膦化合物的合成

以氯金(III)酸(HAuCl4)为起始原料,经过两步反应合成了3种有机膦氯化金化合物,产率均在95%以上。首先HAuCl4与二甲基硫醚(Me2S)反应,制备二甲基硫醚氯化金(I)中间体;然后与有机膦,包括三苯基磷(PPh3)、双(二苯基膦)二茂铁(dppf)、1,2-双(二苯基膦)乙烷(dppe)反应,合成了的三苯基膦氯化金(I)[AuCl(PPh3)]等有机膦氯化金,[AuCl(PPh3)]与三氟甲烷磺酸银(AgSO3CF3)反应,可进一步获得三氟甲烷磺酸三苯基膦金(I)[(CF3SO3)][Au(PPh3)]。     

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。     

Nickel(II), palladium(ii), platinum(ii), and magnesium(ii) fluorene-substituted porphyrinates: Synthesis,structure, and comparative analysis of fluorescence spectra

Using free meso-tetra(2-fluorenyl)porphine (H₂TFP) and nickel(II), palladium(II), and platinum(II) chlorides and an MgBr₂ · Et₂O complex, corresponding metal porphyrinates were synthesized with a high yield. The structures of these new compounds were studied by means of ¹H NMR spectroscopy and electron absorption spectroscopy. The fluorescence spectra of the synthesized compounds in toluene solution were comparatively analyzed. Coordination of Mg²⁺ ion with porphyrinic cycle H₂TFP significantly increases the fluorescence intensity of porphyrinic luminophore; however, the coordination of platinum metal ions (Pt²⁺, Pd²⁺) with tetrapyrrole fragment H₂TPP decreases the fluorescence intensity of porphyrinic cycle and, in the case of nickel ions, fluorescence transitions disappear     

Preparation of silver nanostructure from silver(I) coordination polymer and fabrication of nano silver(I) bromide by reverse micelles technique

A new one-dimensional silver(I) coordination polymer, [Ag(μ-bpfb)(NO₃)]_n (1); bpfb = N,N′-bis(4-pyridylformamide)-1,4-benzene, has been synthesized and characterized by IR, ¹H NMR and ¹³C NMR spectroscopy. The single crystal X-ray data show that the silver(I) 1D coordination polymer grows into a three-dimensional network by hydrogen bonding and π–π stacking interactions. Compound 1 with nanorod morphology was also prepared by sonochemical method. The cetyltrimethylammonium bromide (CTAB) as a cationic surfactant was used in reverse micelles technique to obtain spongy silver(I) bromide nanoparticles from compound 1. Also, different silver nanoparticles have been prepared via direct calcination at 673 K and thermal decomposition in oleic acid from compound 1. The nanostructures of [Ag(μ-bpfb)(NO₃)]_n (1), silver and silver(I) bromide were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray (EDAX) analysis. Thermal stability of compound 1 in both bulk and nano-sized form was studied by thermal gravimetric (TG) and differential thermal (DT) analyses.     

Chiral alkylated poly(m-phenylene)s: Optical activity and thermal stability of helical structures

Chiral poly[4,6-bis(alkylthio)-1,3-phenylene-alt-2-methyl-1,3-phenylene] was synthesized from 1,3-dibromo-2,6-bis(3-dodecyl-2-methylthio)benzene and 2-methyl-1,3-phenylenebis(pinacol borate) as a precursor of chiral poly(thiaheterohelicene). Circular dichroism (CD) spectra that arise from the poly(1,3-phenylene) backbone inverted according to the chirality of the side chains, which indicated that a helical conformation of the polymer was induced by the interaction between the side chains. The CD intensity of the polymer increased in non-polar solvents such as hexane. The decrease in the molar CD intensity and the broadening of a fluorescence band at higher concentrations suggested that the aggregation of the polymer suppressed the formation of the helical structure. The conformational changes were monitored by the CD and the ¹H NMR spectra at different temperatures. In a good solvent such as dichloromethane, the CD intensity increased, and the ¹H NMR signal of benzene protons shifted to lower fields at low temperatures. In hexane, the CD spectra and the ¹H NMR signals were less dependent on temperatures, as a result of the strong interaction between the chiral alkyl chains in the polymer to freeze the helical conformation.     

Oxidation of tungstate‐containing green rust (Cl–) in aqueous solution

The influence of tungstate on the oxidation of green rust [GR(Cl^–)], which contains both Fe(II) and Fe(III), was investigated by synthesizing suspensions of GR(Cl^–) containing tungstate and oxidizing them via injection of N₂ gas containing O₂. XRD and TEM analyses were used for characterizing the solid particles formed during synthesis and oxidation. The results showed that the formation of fine α‐FeOOH was enhanced by the addition of tungstate to the GR(Cl^–) suspensions, while GR(Cl^–) without tungstate was transformed primarily into γ‐FeOOH. The pH, oxidation‐reduction potential (ORP), and dissolved oxygen (DO) values of the aqueous solution were measured during oxidation of GR(Cl^–) with and without tungstate. The results showed that whereas the pH value of the solution was decreased and the ORP value was increased monotonically by oxidation of GR(Cl^–), the pH and ORP values during oxidation the GR(Cl^–) suspension containing tungstate revealed characteristic changes with time. XAS was also used for characterizing the chemical state and local structure of tungstate in the oxidized particles. The results indicated that the local structure of WO was essentially retained in the particles precipitated from GR(Cl^–) suspensions.     

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。     

色层分离法回收锗氯化蒸馏高氯残液中的Zn(Ⅱ)和Cu(Ⅱ)

基于Zn2+/Cu2+与Cl?配位能力的差异,采用阴离子交换色层分离法和717树脂,选择性回收氯化蒸馏提锗工艺所产生高氯残液中的锌和铜.理论计算和光谱分析表明,Zn2+与Cl?的配位能力远强于Cu2+与Cl?的配位能力,同时Cl?浓度显著影响Zn(Ⅱ)和Cu(Ⅱ)在溶液中的存在形态.此外,考察Cl?浓度、树脂用量、振荡...     

甲基丙二酸-(反式-1,2-二甲胺基环丁烷)合铂(II)的合成、结构及抗肿瘤活性

通过水解法合成了甲基丙二酸-(反式-1,2-二甲胺基环丁烷)合铂(Ⅱ)。采用元素分析、质谱(ESI-MS)、红外光谱(IR)和核磁共振氢谱(¹H NMR)确证了该配合物的组成和化学结构。采用MTS法评价其抗肿瘤活性,发现该配合物对常见5种癌细胞的生长有明显的抑制活性。     

A paddlewheel dinuclear Cu(II) compound coordinated with TTF-py redox ligand

A new paddlewheel dinuclear complex with a pyridyl-tetrathiafulvalene (TTF-py) ligand has been obtained and characterized crystallographically as [(DMT-TTF-py)₂Cu₂(OAc)₄]·2C₆H₆ (1). Meanwhile a mononuclear compound [(DMT-TTF-py)₂Cu(PhCOO)₂(CH₃OH)₂]·2CH₂Cl₂ (2) was also isolated. UV–vis spectra and cyclic voltammogram of the paddlewheel complex were studied, showing that compound 1 can undergo an oxidization to form a stable cation of [(DMT-TTF-py)₂Cu₂(OAc)₄]²⁺. By this strategy, compound 3, [(DMT-TTF-py)₂Cu₂(OAc)₄](I₃)₂ as a radical salt, has been prepared and its conductivity of powder sample was 1.02 × 10^?3 ohm^?1 cm^?1. Antiferromagnetic coupling of Cu(II)–Cu(II) was found from the results of ESR spectra, but the coupling between the radical–Cu(II) was very weak.