同、异双核卟啉-Salen型金属配合物的合成及非线性光学性质

设计合成了两种新型卟啉-Salen 型配体5-（3-氨基-4-（3,5-二叔丁基水杨醛基）-氨基苯基）-10,15,20-三苯基卟啉（1）和5-（N,N’-二（3,5-二叔丁基水杨醛基）-3,4-二氨基苯基）-10,15,20-三苯基卟啉（2）及其同、异双核金属配合物和单金属核配合物. 采用氢核磁共振（1H NHR）谱、电喷雾质谱（ESI-MS）、傅里叶变换红外（FTIR）光谱和紫外-可见（UV-Vis）光谱等手段对各目标化合物进行了表征. 用Z扫描技术研究了配体及其金属配合物的三阶非线性光学性质. 实验结果表明：配体1和配体2具有相似的光学特征,均具有反饱和吸收的特性和自散焦效应;当不同的金属离子嵌入配体形成单、双核金属配合物后,分子的极性发生改变,他们的光学特性均受到影响.     

新型不对称卟啉配体及其锌配合物的合成与荧光性能

以3,5-二羟基苯甲酸丙酯和5-(4-硝基)苯基-10,15,20-三苯基卟啉为起始原料,合成了新型的不对称卟啉配体——5-[4-(3,5-二-十六烷氧基苯甲酰亚胺基)苯基]-10,15,20-三苯基卟啉(1)及其锌配合物(2),其结构经UV-Vis,1H NMR,IR和元素分析表征。用荧光激发光谱研究了1和2的荧光性能,结果表明:在激发波长为420 nm时,1和2的荧光发射峰分别在650 nm,709 nm和600 nm,644 nm。     

新型卟啉衍生物的合成、结构表征和电化学性质的研究

以合成的[5-(4-溴苯基)-10,15,20-三苯基卟啉]锌为底物,通Stille偶联的方法合成5-(4’-氨基-4-联苯基)-10,15,20-三苯基卟啉,[5-(4’-氨基-4-联苯基)-10,15,20-三苯基卟啉]锌配合物以及[5- (4’-甲硫基-4-联苯基)-10,15,20-三苯基卟啉]锌配合物。并用Uv,‘H NMR, IR, Ms, Fs等表征确证了该系列配合物的结构,并用循环伏安法对以上部分产物进行了电化学性质的研究.     

酰胺基卟啉的制备,光谱及电化学性质研究

合成了未见文献报道的5-(4-异烟酸酰亚胺基)苯基-10,15,20-三苯基卟啉配体(H2P)及其锌配合物(ZnP),并通过紫外-可见光谱、红外光谱、核磁共振氢谱、元素分析等测试方法对化合物的结构加以确认.研究表明,配体和配合物的拉曼光谱有很大区别,卟啉配体的循环伏安曲线与氨基卟啉和锌配合物不同,卟啉环的氧化还原峰位都有移动.差热研究表明,卟啉配体410oC开始分解,显示了很高的热稳定性.     

卟啉化合物研究(Ⅸ)——聚5-邻丙烯酰胺苯基-10,15,20-三苯基卟啉及其钴配合物的合成

将丙烯酰氯和5-邻氨基苯基-10,15,20-三苯基卟啉(Ⅰ)相连合成了5-邻丙烯酰胺苯基-10,15,20-三苯基卟啉(Ⅱ)。在引发剂作用下,Ⅱ进一步聚合,生成聚5-邻丙烯酰胺苯基-10,15,20-三苯基卟啉(Ⅲ),同时还合成了单体和聚合物的钴配合物。通过元素分析、核磁共振谱、红外光谱和可见吸收光谱对单体和聚合物的结构进行了鉴定。     

5-(4-烟酸酰亚胺基)苯基-10,15,20-三苯基卟啉及其锌配合物的合成及性质研究

合成了未见文献报道的5-(4-烟酸酰亚胺基)苯基-10,15,20-三苯基卟啉配体(H₂P)及其锌配合物(ZnP), 并通过紫外-可见光谱、红外光谱、核磁共振氢谱、元素分析等测试方法对化合物的结构加以确认, 研究了配体和配合物的荧光光谱的变化和电化学性质. 热分析研究表明, 卟啉配体及配合物显示了很高的热稳定性, 超过390 ℃才开始分解.     

非对称结构的Salen型镍、铜、锰配合物的合成及性质

本文设计合成了两种新型Salen配体H2L1(N-苯基-N-(2-羟基-5-甲基苯基)-N′-(2,5-二羟基苯基)-4,5-二甲氧基邻苯二胺)和H2L2(N-苯基-N-(2-羟基-5-甲基苯基)-N′-(2-羟基-3,5二叔丁基苯基)-4,5-二甲氧基邻苯二胺)及相应的过渡金属配合物MLn(M=Ni、Cu、Mn;n=1、2)。分别采用核磁、质谱、元素分析、红外光谱和紫外-可见光谱对目标化合物进行了表征。研究了两种配体及其金属配合物的荧光性质,探讨了配体结构及中心金属离子对其荧光性质的影响。研究发现,由于氢键的作用使得配体H2L1的荧光强度远低于H2L2;中心金属离子的嵌入对H2L2的荧光强度有明显的猝灭作用。用循环伏安法研究了配体及其金属配合物的电化学氧化还原性质,并测定了配体及其金属配合物溶液的电导率、摩尔电导率。结果表明,镍、铜、锰配合物的氧化还原过程均为准可逆的单电子过程;且在所研究的配体和配合物中,金属锰配合物溶液的导电能力较强。     

新型卟啉-席夫碱铜(Ⅱ)/锌(Ⅱ)配合物的合成与光热性能

以吡咯、取代苯甲醛等为原料合成了5-(对-亚苄基亚氨基)苯基-10,15,20-三苯基卟啉的铜(Ⅱ)/锌(Ⅱ)配合物和5-[对-(4-硝基亚苄基亚氨基)]苯基-10,15,20-三苯基卟啉的铜(Ⅱ)/锌(Ⅱ)配合物. 通过FTIR, UV-Vis, 1H NMR, FAB-MS及X射线单晶衍射等手段对产物进行了表征, 并研究了其发光性能及热稳定性. 实验结果表明, 合成配合物的最大发光波长为600 nm, 位于可见光中的红光区; 化合物在空气中的初始分解温度为70 ℃.     

锌卟啉的合成及与咪唑类客体反应的光谱性质

将一对手性丙氨酸,通过烷氧基侧链与卟啉环相连,合成了一对手性卟啉5-对(L-丙氨酰氧乙氧基)苯基-10,15,20-三苯基卟啉和5-对(D-丙氨酰氧乙氧基)苯基-10,15,20-三苯基卟啉及其各自对应的锌卟啉.通过元素分析、紫外-可见光谱、1 H核磁共振和红外光谱等方法对合成的自由卟啉及锌卟啉配合物进行了结构确定.此外,采用荧光光谱滴定实验研究了金属锌卟啉与咪唑类客体进行配位反应的光谱性质,结果表明,咪唑类客体与手性锌卟啉相互作用时均具有荧光猝灭效应,金属卟啉的手性结构对该性质未造成影响.     

新型桥连双卟啉化合物的合成及结构表征

通过将4,4′-二羧基-2,2′-联吡啶、2,6-二溴甲基吡啶、2,6-二羟甲基吡啶和1,8-二氨基萘分别与5-(4-羟基苯基)-10,15,20-三苯基卟啉(1a)、5-(4-甲酰苯基)-10,15,20-三苯基卟啉(1b)和5-[4-(4′-溴代丁氧基)苯基]-10,15,20-三苯基卟啉(1c)反应,合成了3类新型的双卟啉化合物2a-2e,经IR,¹HNMR,MS,UV-Vis光谱及元素分析对中间体和目标化合物的结构进行了表征.     

5-氟尿嘧啶修饰卟啉的合成及抗肿瘤活性

合成了一种5-氟尿嘧啶修饰的自由卟啉(5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)卟啉)及其2种金属卟啉配合物:5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)锰卟啉和5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)锌卟啉。 通过紫外可见光谱(UV-Vis)、红外光谱(IR)和核磁共振谱氢谱(¹H NMR)对目标化合物进行了结构表征。 用噻唑蓝法(MTT法)测定了自由卟啉、锰卟啉及锌卟啉分别对肺腺癌细胞株A549、肝癌细胞株Bel7402和人结肠癌细胞株HCT-8的抑制活性。 其中,锰卟啉对人结肠癌细胞株HCT-8的半抑制浓度为IC₅₀为17.8 mg/L,具有一定的细胞毒作用。     

Synthesis, physico-chemical studies and solvent-dependent enantioselective epoxidation of 1,2-dihydronaphthalene catalysed by chiral Ruthenium(II) Schiff base complexes. I

Ruthenium(II) chiral Schiff base complexes 1–10 and their precursor ligands derived from -amino acids viz. -leucine, -histidine with salicylaldehyde, 3-tertiary-butyl-, 3,5-di-tertiary-butyl-, 3,5 dichloro- and 3,5-dinitrosalicylaldehyde are reported. The characterization of the ligands and complexes was accomplished by various appropriate physico-chemical studies, namely, microanalysis, IR-, UV/Vis-, ¹H, ³¹P{¹H} NMR, CD spectroscopy, optical rotation, conductance measurement and cyclic voltammetry. The complexes thus synthesised were used as catalysts for enantioselective epoxidation of 1,2-dihydronaphthalene. The effect on enantioselectivity and chemical conversions to epoxide were studied in different solvents viz. acetonitrile, dichloromethane and fluorobenzene along with change of the substituents on ligands and different terminal oxidants. The less polar nature of solvent as well as the donating group attached on the catalysts favours enantioselectivity, while PhIO was the oxidant of choice. The enantiomeric excess of the resulting epoxide was evaluated by chiral cyclodex BDA capillary column.     

Salen型化合物的合成、表征及性质

设计合成了两种新型Salen配体H2L1(N,N?-3-二甲氧基-邻羟苯亚甲基-4,5-二甲氧基-1,2-苯二胺)、H2L2(N,N?-3-二甲氧基-邻羟苯亚甲基-4,5-二硝基-1,2-苯二胺)及相应的镍、铜、锌金属配合物ML1、ML2(M=Ni,Cu,Zn),并分别采用核磁共振(1HNMR)波谱、紫外-可见(UV-Vis)吸收光谱、红外(IR)光谱、质谱(MS)和元素分析进行了表征.探究了配体及其配合物的荧光性质.研究发现,与H2L1相比,配体H2L2由于引入强的吸电子基团―NO2,其荧光强度减弱.相对于配体,锌离子的配位则导致其配合物的荧光强度增强,而镍和铜离子的嵌入则使得配合物ML1、ML2(M=Ni,Cu)荧光猝灭.对电化学性质的研究表明,CuL1的氧化还原过程为准可逆的单电子过程;与H2L2相比,配体H2L1由于引入强的给电子基团―OCH3,其溶液的导电性降低.     

硫代多联吡啶铂(Ⅱ)配合物的合成、性质及在光催化制氢中的应用

合成了2个新配体4-(4-硫代乙酸)甲苯基-6-苯基-2,2'-联吡啶HC^N^N(PhCH₂SCOCH₃)(L3)和6-(4-硫代乙酸)甲苯基-2,2'-联吡啶 HC^N^N (CH₂SCOCH₃)(L5)及其发光的铂(Ⅱ)配合物ClPtC^N^N(PhCH₂SCOCH₃)(C3)和ClPtC^N^N(CH₂SCOCH₃)(C5). 通过¹H NMR谱和质谱对它们的结构进行了表征, 采用X射线单晶衍射分析确定了C3的晶体结构. 利用紫外-可见吸收光谱、 发射光谱及激发态寿命测定研究了它们的光物理性质和电化学性质, 以及配合物作为光敏剂在光催化制氢中的应用. 通过系列配合物产氢效率的比较, 揭示了它们的产氢效率和激发态寿命的关系.     

Mononuclear manganese carboxylate complexes: Synthesis and structural studies

Several manganese carboxylates complexes having Pz^iPr2H (3,5-diisopropylpyrazole), Tp^Ph,Me (hydrotris(3-phenyl,5-methyl-pyrazol-1-yl)borate), Tp^ipr2 (hydrotris(3,5-diisopropyl-pyrazol-1-yl)borate) as supporting ligands have been synthesised and structurally characterized. Single-crystal X-ray diffraction studies suggest that the manganese center in complexes (Pz^iPr2H)₄Mn(NO₂–OBz)₂ (5) and (Pz^iPr2H)₄Mn(F–OBz)₂ (6) have same coordination environment and geometry whereas the complex [Tp^Ph,MeMn(OAc)Pz^Ph,MeH] (7) has a five coordinate manganese center. In all these complexes, the carboxylate groups are coordinated as monodentate and the uncoordinated oxygen atom of the carboxylate groups form intramolecular hydrogen bonds with the NH group of the corresponding coordinated pyrazole (Pz^iPr2H/Pz^Ph,MeH). The complexes 5–8 and 10 were tested for their superoxide dismutase activity and it was found that only complex 7 has SOD activity as its structure is very similar to the active site structure of the native Mn–SOD enzyme. The SOD activity studies on these carboxylate complexes suggest that any model compound with analogous active site structure and intramolecular hydrogen bonding may be a suitable mimic for the Mn–SOD enzyme.     

o-Alkyl-substituted aromatic phosphanes for hydroformylation studies: synthesis, spectroscopic characterization and ab initio investigations

In earlier hydroformylation studies modification of the rhodium catalyst with o-methyl-substituted or o-ethyl-substituted phosphane ligands have increased regioselectivity to branched aldehydes. The promising results achieved created a need for further studies. Hence, a wider group of o-substituted arylphosphane ligands, e.g. (2-cyclohexylphenyl)diphenylphosphane, (2-isopropylphenyl)diphenylphosphane, (2-methylnaphthyl)diphenylphosphane, (2,5-dimethylphenyl)diphenylphosphane and (2-phenylphenyl)diphenylphosphane were synthesized and tested in rhodium-catalyzed hydroformylation to support the previous findings. Characterization of the ligands was made by NMR spectroscopy (¹H, ³¹P{¹H}, ¹³C{¹H}, HSQC, COSY-90 and COLOC). Additional parameters for evaluation of the stereoelectronic properties of the ligands were provided by quantum mechanical calculations and by synthesizing Rh(acac)(CO)(PR₃) complexes. In the rhodium-catalyzed hydroformylation of propene and 1-hexene the ligands increased the formation of branched aldehydes compared to triphenylphosphane. Additionally the increasing size of the o-alkyl-substituent was found to effect favorably to the iso-selectivity.     

X-ray structure and multinuclear NMR studies of platinum(II) and palladium(II) complexes with 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine

Pt(II) and Pd(II) dichloride complexes with 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) have been synthesized and characterized by infrared and ¹H, ¹³C NMR, ¹³C CPMAS spectroscopy. The structures of the cis-PtCl₂(dbtp)₂ · EtOH (1) and cis-PdCl₂(dbtp)(dmso) (2) has been determined by signal-crystal X-ray diffraction. In both complexes the X-ray crystal structures shows that heterocycle ligand (dbtp) binds the central atom monodentate via nitrogen atom N(3). In addition, compound (2) is interesting for its structural features, because it is the first report of mixed dichloride Pd(II) complexes with N-donor (triazolopyrimidine) and S-donor (dimethylsulfoxide) ligands. In this structure the Pd–Cl distances are: 2.302(1) and 2.281(1) Å, Pd–N 2.041(3) Å and Pd–S 2.245(1) Å. The ¹H, ¹³C NMR studies show clearly that these structures are retained in solution.     

双(取代水杨醛)缩卡巴肼正丁基锡配合物的合成、结构及除草活性

在微波甲醇溶剂热中,正丁基三氯化锡(n-BuSnCl₃)与双[4-二乙氨基或(3,5-二叔丁基)取代水杨醛]缩卡巴肼和缩硫代卡巴肼配体反应,合成双(取代水杨醛)缩卡巴肼和缩硫代卡巴肼丁基锡配合物,( n-BuSn) ₂CI₃(OH₂)[(2-OH,R)PhCH=NNH]₂CX[R:4-NEt₂(4-二乙氨基),X:O(A1);R:4-NEt₂,X:S(A2);R:3,5-(t-Bu)₂,X:O(A3);R:3,5-(t-Bu)₂,X:S(A4)],经元素分析、IR、¹H 和 ¹³C NMR表征,X射线衍射获得的配合物A2的晶体结构表明,化合物A2是具有六配位畸形八面体构型的双锡核配合物。 配体及其丁基锡配合物均对马齿苋、刺苋、四九菜心、苋菜和决明子靶标植物具有生长抑制作用,且配合物A1和A2具有较广谱、配合物A3和A4具有选择性生长抑制作用,可作为杂草生长抑制候选物研究。     

Mono- and dinuclear ruthenium complexes of bridging ligands incorporating two di-2-pyridylamine motifs: Synthesis, spectroscopy and electrochemistry

Mono- and dinuclear ruthenium(II) complexes of six bridging ligands that contain a central arene (phenyl, naphthalenyl or biphenyl) core to which are attached two di-2-pyridylamine groups have been prepared. These complexes possess six-membered chelate rings. Full assignments of their ¹H NMR spectra are described which provides insight into the comformations of the ligands in these complexes. The extent of metal–metal communication in the dinuclear complexes was probed by electrochemical measurements and related to metal–metal distances.