新型卟啉及其锌配合物的合成与性质研究

设计合成了一种新型的不对称卟啉(5,10,15-三苯基-20-{4-[6′-(4″-o-亚水杨基)-苯亚胺基]己氧基}苯基卟啉)及其锌配合物,并用¹H NMR、质谱及紫外-可见光谱进行表征。采用紫外-可见光谱滴定法,对锌卟啉与4种咪唑类小分子间的轴向配位反应热力学性质的研究表明：反应为放热、熵增加过程,4种咪唑类配体对锌卟啉的配位平衡常数按K^Θ(2-MeIm)>K^Θ(N-MeIm)>K^Θ(2-Et-4-MeIm)>K^Θ(Im)顺序依次减小。运用Z-扫描技术研究了新型卟啉及其锌配合物的非线性光学性质。     

两种1,2,3-三唑衍生物的配合物合成策略:晶体结构和表面分析

在不同反应条件下反应得到了两种1,2,3-三唑衍生物的配合物[Co（H₂O）₆][Co（L¹）₃]₂·4H₂O（1）和Cu（L²）₂（2）（HL¹=5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid;HL²=1-（4-iodophenyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）。通过X射线单晶衍射和红外光谱确定了晶体结构,同时对配合物1和2进行了表面作用分析（Hirshfeld surface analysis）,在二维指纹图谱中可以清楚的看到配合物中的主要分子间作用。     

含两个酰胺基团的卟啉二聚体分子间氢键引起的发光光谱红移

通过5-（4-甲酸基苯基）-10,15,20-三（4-十二烷氧基苯基）卟啉（HAcTPP）与乙二胺,丙二胺和丁二胺反应,制备了一类含2个酰胺基团的卟啉二聚体C₂（AmTPP）₂、C₃（AmTPP）₂和C₄（AmTPP）₂以及相应的配合物Pt2C₂（AmTPP）₂、Pt2C₃（AmTPP）₂和Pt2C₄（AmTPP）₂。采用¹H NMR、¹³C NMR、质谱、元素分析、循环伏安、紫外-可见吸收光谱和荧光发射光谱等对二聚体的化学结构、热稳定性、电化学和光物理性质进行了表征。实验发现,二聚体和相应的铂配合物的光致发光（PL）光谱性质与溶液的浓度有关,在10^-7 mol·L^-1 THF稀溶液中,二聚体与单羧基卟啉的PL光谱基本一致。当浓度增加到10^-3 mol·L^-1 THF溶液时,二聚体的光致发光光谱最大值从657 nm红移到675 nm,比单羧基卟啉红移了18 nm。当与金属铂配位后,这种发射光谱随浓度增加而变化的特性更加明显。二聚体配合物在10^-7 mol·L^-1 THF稀溶液中PL光谱就产生了红移现象,最大发射峰λ_max为673 nm,比单羧基卟啉红移16 nm。在高浓度10^-4 mol·L^-1 THF溶液和升华薄膜中的PL最大发射峰进一步红移到727 nm的近红外区。进一步,为了证实二聚体配合物分子间的π-π和Pt-Pt相互作用,我们以配合物Pt2C₃（AmTPP）₂为例,对二聚体配合物固体在常温和低温77 K的PL光谱进行了测试,发现固体配合物表现出与温度相关的PL性质。当温度降到77 K时,配合物的最大发射峰从658 nm红移到674 nm,红移了16 nm。实验表明,卟啉二聚体和相应的配合物的红移现象与二聚体的分子结构直接相关,卟啉二聚体中的两个酰胺基团能够产生较强的分子间氢键,导致二聚体分子之间产生一定程度的π-π和Pt-Pt相互作用,使得二聚体PL光谱产生红移。     

系列单取代烷氧基-2-羟丙基-β-环糊精的合成与表征

以环氧氯丙烷和脂肪醇为原料, 通过相转移催化法合成了乙基、正丙基、正丁基和正戊基缩水甘油醚(1～4), 并利用所合成的缩水甘油醚和β-环糊精为原料, 分别在弱碱水溶液(1.5%)和强碱水溶液(30%)中制备并用硅胶柱分离出单2位取代的乙氧基、丙氧基、丁氧基和戊氧基-2-羟丙基-β-环糊精(1a～4a)和单6位取代的丙氧基、丁氧基和戊氧基-2-羟丙基-β-环糊精(2b～4b), 利用薄层色谱、红外光谱、差热扫描量热分析、质谱和核磁共振等手段对所合成的产品进行了表征.     

R6G@γ-CD-MOFs复合物的制备及其在Fe3+离子传感中的应用

利用γ-环糊精（γ-CD）、氢氧化钾、甲醇和水,制备了γ-CD-MOFs,并使用X射线粉末衍射、热重分析和扫描电镜对其结构、稳定性和形貌进行表征。由于γ-CD-MOFs的结构中含有一维孔道,在其孔道中引入黄光发射的罗丹明6G （R6G）染料,获得了荧光复合材料R6G@γ-CD-MOFs,并探索了其对不同金属离子的荧光响应情况。实验结果表明,R6G@γ-CD-MOFs能够从12种金属离子中选择性传感Fe³⁺离子,在2×10^-4~2.0×10^-2 mol·L^-1范围内其荧光猝灭常数（K^sv）为1.03×10⁴ L·mol^-1。     

以3,5-二（吡啶-4-甲氧基）苯甲酸为配体构筑的两个钡（Ⅱ）、铅（Ⅱ）配位聚合物

以3,5-二（吡啶-4-甲氧基）苯甲酸（HL）为配体合成了2个配合物：[BaL₂]_n（1）和[PbL（Ox）_0.5]_n（2）（H₂（Ox）为草酸）,并通过元素分析,红外光谱,热重和X-射线单晶衍射实验对其结构进行了表征。分析表明,1由L^-连接形成二维结构,通过苯环之间的π…π作用连接成三维网络结构;2由于主配的连接形成二维层状结构,再通过辅配连接形成拓扑符号为（4³）（4⁴.5.6¹⁷.7².8²）（4.5²）的三维网络结构。     

新型手性<i>β</i>-烷氨基-<i>γ</i>-(<i>l</i>-孟氧基)丁内酯的合成

脂肪族伯胺作为亲核试剂与手性合成子5(R)-(l-孟氧基)-2(5H)-呋喃酮(4)发生不对称Michael加成反应, 得到一系列新的手性β-烷氨基-γ-(l-孟氧基)丁内酯类化合物6(产率34～81%, de≥98%). 通过IR, ¹H NMR, ¹³C NMR, MS, 元素分析及单晶X射线衍射分析, 确认了它们的化学结构、立体化学和绝对构型. 此结果为某些具有生物活性化合物及复杂分子的合成提供了新的途径.     

基于双核{Zn2(COO)4}次级构筑单元的二维发光配位聚合物的晶体结构和对Fe3+的检测

使用H2L配体（H2L=2-（1,3-dioxo-1H-benzo[de]isoquinolin-2（3H）-yl） terephthalic acid）和Zn²⁺通过水热反应,合成了一例基于双核{Zn₂（COO）₄}次级构筑单元的二维发光配位聚合物[Zn₂（L）₂（DMSO）₂（DMF）]（1）（DMSO=二甲亚砜,DMF=N,N-二甲基甲酰胺）。拓扑分析表明1结构中的双核{Zn₂（COO）₄}单元可视为4连接节点,并与作为连接子的L^2-形成（4,4）-网拓扑构型。1表现出对Fe³⁺离子的选择性发光猝灭响应,检测限为2.8 μmol·L^-1。1对Fe³⁺的检测具有良好的抗干扰性,且可通过DMF溶剂洗涤实现再生,可多次循环使用。     

环糊精-苯丙氨酸超分子体系的包合现象与分子识别

通过紫外-可见光谱探讨了水溶液中α-环糊精(CD 1),β-CD 2,七(2, 6-二-o-甲基)-β-CD 3和γ-CD 4与D-、L-、D,L-苯丙氨酸(Phe)形成超分子包合物的稳定常数(K)。手性或外消旋苯丙氨酸与同一主体结合能力的强弱顺序为:L- >D,L- >D-Phe,各体系的K_L/K_D值在1.65～3.01之间,给出了较好的异构体分离。但三种形式的苯丙氨酸与这些主体的缔合常数均较小(K< 3×10²mol·L^-1)。就不同主体而言,K值的次序为:3 >1 >4 >2,并不完全等同于K_L/K_D的顺序:2 >1 >3 >4。     

基于碳纳米管负载的电催化剂高效检测还原型谷胱甘肽

通过两步法合成了10-甲基吩噻嗪/2-羟丙基-β-环糊精主客体化合物修饰的多壁碳纳米管复合材料MPT-HP-β-CD/MWNT,并用FT-IR、UV-Vis、荧光光谱、拉曼光谱、TEM等对其组成进行表征。通过CV曲线、i-t曲线对谷胱甘肽（GSH）的催化性能以及对催化剂阻抗的研究,证明了MWNT可以提高导电能力,提高对GSH的催化活性。此外,还研究了pH值、温度、扫速等对催化剂催化活性的影响,表明该复合材料可用于GSH的电化学检测,并具有良好的稳定性、重现性以及很高的灵敏度。最优检测浓度范围为5×10^-7~4.95×10^-5 mol·L^-1,检测限为3.96×10^-8 mol·L^-1（S/N=3）。     

Syntheses,characterizations, and antimicrobial activities of binuclear ruthenium(III) complexes containing 2-substituted benzimidazole derivatives

Binuclear ruthenium(III) complexes [RuX₃L]₂?·?nH₂O (X?=?Cl, L?=?L¹, L², L³; n?=?1, L⁴ and L⁵, X?=?Br; L?=?L³), [RuX₃L_1.5]₂?·?nH₂O (X?=?Br, L?=?L¹; n?=?0, L⁴; n?=?6 and L⁵; n?=?10), and [RuX₃L₂]₂ (X?=?Br, L?=?L²) have been isolated by treatment of hydrated RuX₃ (X?=?Cl/Br) in acetone with 2-(2′-aminophenylbenzimidazole) (L¹), 2-(3′-aminophenylbenzimidazole) (L²), 2-[(3′-N-salicylidinephenyl)benzimidazole] (L³), 2-(3′-pyridylbenzimidazole) (L⁴), and 2-(4′-pyridylbenzimidazole) (L⁵) in acetone. The complexes were characterized by elemental analysis, conductivity and magnetic susceptibility measurements, IR, electronic, EPR, and mass spectral studies. The complexes were dimeric; based on analytical and spectral studies, an octahedral geometry was proposed for the complexes. The synthesized complexes were screened against Gram-positive and Gram-negative bacteria and fungi.     

酰腙类Schiff碱汞(Ⅱ)配合物的合成及晶体结构

合成了Schiff碱配体3-乙酰吡啶缩邻氨基苯甲酰腙(L¹)及4-乙酰吡啶缩邻氨基苯甲酰腙(L²),并分别与HgCl₂进行了配位反应,得到2个配位聚合物{[Hg(L¹)Cl₂]·CH₃OH}_n (1)和[Hg(L²)Cl₂]_n (2),采用¹H NMR、FTIR和元素分析等手段对化合物进行了表征,并对配合物的热稳定性进行了考察。通过X射线单晶体衍射技术测定了2个配合物的单晶结构,结构解析表明,配合物1属于三斜晶系,P1空间群,配合物2属于单斜晶系,P2₁/n空间群。     

Acridine N-Heterocyclic Carbene Gold(I) Compounds: Tuning from Yellow to Blue Luminescence

The synthesis and the luminescence features of three gold(I)-N-heterocyclic carbene (NHC) complexes are presented to study how the n-alkyl group can influence the luminescence properties in the crystalline state. The mononuclear gold(I)-NHC complexes, [( L¹ )Au(Cl)] ( 1 ), [( L² )Au(Cl)] ( 2 ), and [( L³ )Au(Cl)] ( 3 ) were isolated from the reactions between [(tht)AuCl] and corresponding NHC ligand precursors, [N-(9-acridinyl)-N’-(n-butyl)-imidazolium chloride, ( L¹ .HCl)], [N-(9-acridinyl)-N’-(n-pentyl)-imidazolium chloride, ( L² .HCl)] and [N-(9-acridinyl)-N’-(n-hexyl)-imidazolium chloride, ( L³ .HCl)]. Their single-crystal X-ray analysis reveals the influence of the n-alkyl groups on solid-state packing. A comparison of the luminescence features of 1 – 3 with n-alkyl substituents is explored. The molecules 1 – 3 depicted blue emission in the solution state, while the yellow emission (for 1 ), greenish-yellow emission (for 2 ), and blue emission (for 3 ) in the crystalline phase. This paradigm emission shift arises from n-butyl to n-pentyl and n-hexyl in the crystalline state due to the carbon-carbon rotation of the n-alkyl group, which tends to promote unusual solid packing. Hence n-alkyl group adds a novel emission property in the crystalline state. Density Functional Theory and Time-Dependent Density Functional Theory calculations were carried out for monomeric complex, N-(9-acridinyl)-N’-(n-heptyl)imidazole-2-ylidene gold(I) chloride and dimeric complex, N-(9-acridinyl)-N’-(n-heptyl)imidazole-2-ylidene gold(I) chloride to understand the structural and electronic properties.     

Synthesis,crystal structures,fluorescence, electrochemiluminescent properties,and Hirshfeld surface analysis of four Cu/Mn Schiff-basecomplexes

Four new complexes [Cu(L¹)₂]_n ( 1 ), [Mn(L¹)₂]_n ( 2 ), [Cu(L²)₂]_n ( 3 ), [Mn(L²)₂]_n ( 4 , HL¹ = 2-(((4H-1,2,4-triazol-4-yl)imino)methyl)-4,6-dichlorophenol; HL ² = 2-(((4H-1,2,4-triazol-4-yl)imino)methyl)-4,6-dibromophenol) were synthesized by microreaction bottle method. Complexes 1 and 3 and 2 and 4 are isomorphous heterostructures having the same molecular structure. The structures of 1 – 4 were characterized using single X-ray diffraction, Fourier-transform infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analysis, and their potential applications were analyzed by detecting their fluorescence and electrochemical luminescence (ECL). Hirshfeld surface analysis indicates that X···H (X = Br, Cl) interactions play a crucial role in stabilizing the self-assembly process of 1 – 4 , which show highly intense ECL in N,N-dimethylformamide solution and high thermal stability.     

酰腙类Schiff碱汞(Ⅱ)配合物的合成及晶体结构

合成了Schiff碱配体3-乙酰吡啶缩邻氨基苯甲酰腙(L1)及4-乙酰吡啶缩邻氨基苯甲酰腙(L2),并分别与Hg Cl2进行了配位反应,得到2个配位聚合物{[Hg(L1)Cl2]·CH3OH}n(1)和[Hg(L2)Cl2]n(2),采用1H NMR、FTIR和元素分析等手段对化合物进行了表征,并对配合物的热稳定性进行了考察。通过X射线单晶体衍射技术测定了2个配合物的单晶结构,结构解析表明,配合物1属于三斜晶系,P1空间群,配合物2属于单斜晶系,P21/n空间群。     

十八烷基-L-苯丙氨酸齐聚物在有机溶剂中的自组装

由L-苯丙氨酸和二(三氯甲基)碳酸酯反应得到的L-苯丙氨酸-N-羧基-环内酸酐(L-Phe-NCA), 在十八胺的引发下开环聚合得到十八烷基-L-苯丙氨酸齐聚物(简称L-Phe-R18). ¹H NMR (300 MHz)和FT-IR表征了产物结构, 是平均聚合度为5的齐聚物. L-Phe-R18能在多种有机溶剂中发生聚集和自组装, 并进而在这些有机溶剂中形成热可逆的物理凝胶. 其中, 该齐聚物能在氯苯、二苯醚、甲苯等溶剂中形成透明凝胶. 也能在苯、硝基苯、醋酸丁酯等溶剂中形成非透明凝胶. L-Phe-R18在这些有机溶剂中的最低凝胶化浓度(MGC)在w＝0.3%～1%之间. X射线衍射(XRD)数据和场发射扫描电镜(FE-SEM)以及分子模拟表征了L-Phe-R18聚集体的微观形态和可能的聚集方式. 认为L-Phe-R18在有机溶剂中通过分子间氢键、π-π堆积等非共价键相互作用聚集、组装成厚度约为20 nm左右的带状纤维, 溶剂分子以毛细力存在于相互缠绕的纤维网络结构中, 使体系形成稳定的凝胶.     

Synthesis,spectroscopic and thermal properties of Pt(II) complexes of some polydentate ligands

The new tetradentate symmetrical (2R,2′S)-1,1′-piperazine-1,4-diyldipropane-2-thiol) (L¹), (2S)-1-[bis(2-aminoethyl)amino]propan-2-ol) (L²), and 2-{(E)-[((1R,2S)-2-{[(1Z)-(2-hydroxy phenyl)methylene]amino}cyclohexyl)imino]methyl}phenol (L³) ligands were synthesized and characterized on the basis of FT-IR, ¹H, ¹³C NMR, EI mass, and elemental analysis. Three commercially available ligands, (2,2′-[ethane-1,2-diylbis(thio)]diethanol (L⁴), 2,2′-dithiodiethanenamine (L⁵), and (2,2′-[ethane-1,2-diyldi(imino)] diethanol (L⁶), were also studied. Pt(II) complexes were characterized by FTIR, elemental analysis and thermal methods. Thermal behaviors of these complexes were investigated in the range 10–1000 °C. Magnetic properties were also studied, and the all complexes were found to be diamagnetic. The structures consist of the monomeric units in which the Pt(II) atoms exhibit square planar geometry. N,N′-bis(salicylidene)-1,2-cyclohexane has been synthesized and characterized by X-ray single crystal diffraction measurement. The ligand crystallizes in monoclinic crystal system and space group, Cc.     

Substitutions of organopalladium(II) species with benzimidazole derivatives

The [Pd(cod)(cotl)]ClO₄ complex (cod = cycloocta-1,5-diene; cotl = cyclooctenyl, C₁₈H₁₃ ^–) undergoes substitutions with new Schiff base ligands containing benzimidazole L [L = 2-(2-N-n-propylidenephenyl)benzimidazole (L¹); 2-(2-N-i-propylidenephenyl)benzimidazole (L²); 2-(2-N-n-butylidenephenyl)benzimidazole (L³); 2-(2-N-i-butylidenephenyl)benzimidazole (L⁴)]. Facile displacement of cod by L occurs to produce complexes of the type [Pd(cotl)L]ClO₄· nMe₂CO (n= 0; L = L¹, L² or L³; n= 2, L = L⁴). Dihalobridge complexes of the type [Pd(cotl)X]₂(X = Cl or Br) undergo halogen-bridge cleavage with L¹–L⁴ to give mononuclear complexes of the type Pd(cotl)LX · nH₂O (n= 2, X = Cl, L = L¹; n= 0, X = Br, L = L¹; n= 0, X = Cl, L = L²; n= 0, X = Cl or Br, L = L³; n= 0, X = Cl, L = L⁴; n= 2, X = Br, L = L⁴) and a binuclear complex [Pd(cotl)Br]₂L². The complexes were characterised by physical properties, i.r., ¹H- and ¹³C-n.m.r. spectral techniques and by mass spectra. Probable structures have been proposed.     

Polymer supported 5,10,15,20-tetrakis(phenoxy acetic acid)porphyrin derivative for separation and preconcentration of d- and f-electron metals

5,10,15,20-tetrakis(phenoxy acetic acid) porphyrin (PAAP) was covalently linked to Merrifield chloromethylated resin. Characterization of PAAP and the modified polymeric matrix were performed by ¹H NMR, FTIR and elemental analysis. The sorbent was used for the separation and enrichment of the d-electron metals (Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)) at pH 6–8 and of the f-electron metals U(VI) and Th(IV) at pH 4–5. The metals ions were preconcentrated with a concentration factor range of 115–215 and then determined by flame atomic absorption spectrometry or visible spectrophotometry using Arsenazo(III). The retained metals were eluted with 2.0 mol L⁻¹ HNO₃ in the case of the d-electron metals and 0.1/0.25 mol L⁻¹ HCl in the case of the f-electron metals. The procedure was validated by analyzing the NIST standard reference material 2709 (San Joaquin Soil). Correspondence: Melek Merdivan, Chemistry Department, Faculty of Arts and Sciences, Dokuz Eylul University, 35160 Buca, Izmir, Turkey