Cobalt complexes based on dendritic PAMAM bridged salicylaldimine ligands: Synthesis,characterization and performance in ethylene oligomerization

Two novel dendritic poly(amido-amine) (PAMAM) bridged salicylaldimine ligands were synthesized by Schiff base reaction using 1.0 generation dendritic PAMAM as bridged groups. The cobalt complex with 1,4-butanediamine as core (C1) and the cobalt complex with 1,6-hexanediamine as core (C2) based on dendritic PAMAM bridged salicylaldimine ligands were prepared by metallic coordination reaction, respectively. The structures of the ligands and the dendritic cobalt complexes were characterized by fourier transform infrared (FTIR), ultraviolet spectra (UV), hydrogen nuclear magnetic resonance (¹H NMR) and electrospray ionization mass spectra (ESI-MS). The complexes C1 and C2 were evaluated as catalyst precursors for ethylene oligomerization after being activated with methylaluminoxane (MAO), diethylaluminum chloride (Et₂AlCl), ethylaluminium dichloride (EtAlCl₂) and ethylaluminum sesquichloride (EASC). The dendritic cobalt complexes exhibited the highest activity and selectivity for high carbon oligomers with EASC as activator. Under the conditions of 1.0 MPa, 25°C and Al/Co molar ratio 1500, the catalytic activity and selectivity for C₁₀–C₂₀ using C1 were 3.44×10⁶ g·(mol Co·h)^?1 and 76.53% after activation with EASC, and the catalytic activity and selectivity for C₁₀–C₂₀ using C2 were 3.42×10⁶ g·(mol Co·h)^?1 and 84.50%, respectively.     

两个基于4-(1H-1,2,4-三氮唑)苯甲酸的4d-4f异核配位聚合物的合成、结构及荧光性质

以4-(1H-1,2,4-三氮唑)苯甲酸(Htbc)为配体,采用水热法合成了两种新型4d-4f配位聚合物{[EuAg(tbc)₃(H₂O)]ClO₄·H₂O}_n(1)和{[Eu₂Ag₃(tbc)₆(NO₃)₂(H₂O)₂](ClO₄)₂·2H₂O}_n(2)。运用X射线单晶衍射法对该配位聚合物进行了结构测定,并对其进行了元素分析、红外光谱、PXRD及荧光光谱表征。单晶结构表明,配位聚合物1为正交晶系,空间群P2₁2₁2₁,由一维三股螺旋链(其中2股右手螺旋和1股左手螺旋)通过Ag将其连成二维平面。配位聚合物2属于三斜晶系,空间群为P1,由内消旋一维两股螺旋链通过Ag将其连成二维平面。配位聚合物1和2的二维链结构均通过非共价键作用形成三维超分子, 同时也表征了配位聚合物1和2的荧光性质。     

由羧酸配体和铁(Ⅱ)构筑的两个过渡金属配位聚合物的结构、表征和性质

采用水热法合成了2个铁的过渡金属配位聚合物[Fe(Medpq)(BDC)H₂O]_n(1)和{[Fe(Medpq)(QUI)H₂O]·2H₂O}_n(2)(Medpq=2-methyldipyrido[3,2-f:2',3'-h]quinoxaline; H₂BDC=terephthalic acid; H₂QUI=2,3-pyridinedicarboxylic acid),并对其进行了元素分析、红外光谱和热重表征,并用X射线单晶衍射测定结构。2个配位聚合物中的中心铁(Ⅱ)离子,都呈现一个稍微扭曲的八面体几何构型。     

三个喹啉氧基乙酰胺镧系(Eu、Gd、Er)配合物的合成、结构及Eu配合物的荧光性质

合成并通过单晶衍射表征了3个稀土配合物Ln(L)(NO₃)₃(H₂O)(L=N-苯基-2-(5-氯-8-喹啉氧基)乙酰胺,Ln=Eu(1),Gd(2),Er(3)),结构与拥有相同有机配体的Pr,Nd和Sm配合物同构。在每个配合物中,十配位的稀土离子采取扭曲的双帽四方反棱柱配位构型,分别与来自1个配体L的2个氧原子和1个氮原子,3个双齿配位硝酸根和1个水分子配位。配合物1能够发射Eu(Ⅲ)离子特征荧光,荧光寿命为437 μs。     

镧系元素(La、Tb、Dy)的喹啉氧基乙酰胺配合物的结构及荧光性质

合成并通过单晶衍射表征了3个稀土配合物[LaL₂(NO₃)₃]·CH₃CN(1),[Ln(L)(NO₃)₃(H₂O)](Ln=Tb(2),Dy(3),L=N-苯基-2-(5-氯-8-喹啉氧基)乙酰胺)。在配合物1中,十二配位的La(Ⅲ)离子采取扭曲的二十面体配位构型,分别与来自2个酰胺配体L的4个氧原子和2个氮原子,及3个双齿配位硝酸根配位。配合物2和3的结构与拥有相同有机配体的Pr、Nd、Sm、Eu、Gd和Er配合物同构。在每个配合物中,十配位的稀土离子与来自1个配体L的2个氧原子和1个氮原子,3个双齿配位硝酸根和1个水分子配位,拥有扭曲的双帽四方反棱柱配位构型。固态配合物2和3在可见区发射强荧光。     

Synthesis of Unsymmetrical 1,3‐Diynes via Pd/Cu‐Catalyzed Cross‐Coupling of Terminal Alkynes at Room Temperature

A facile and practical synthetic route of unsymmetrical 1,3‐diynes via the PdCl/CuI catalyzed oxidative coupling of two different terminal alkynes has been developed by using 3‐(diphenylphosphino)propanoic acid as a ligand in the presence of oxygen. This system is suitable for not only aromatic alkynes but also heteroaromatic and aliphatic alkynes which were transformed into the corresponding unsymmetrical 1,3‐diynes in moderate to good yields at room temperature. Moreover, the unsymmetrical 1,3‐diynes were also obtained on a multi‐gram scale. Mechanistic studies suggest that oxygen plays a key role in the catalytic cycles.     

喹啉类单核锰(Ⅱ)和钴(Ⅱ)配合物的合成、结构、DNA/BSA键合及DNA切割活性

合成了2个结构类似的喹啉类单核锰和钴配合物[ML（H₂O）₃]·H₂O,其中M为Mn（1）、Co（2）,Na₂L为8-（羧基钠甲氧基）喹啉-2-甲酸钠。运用红外光谱、元素分析和X射线单晶衍射表征了其结构。利用电子吸收和发射光谱法研究了配合物与CT-DNA及BSA的键合作用及配合物对DNA的切割作用。晶体解析结果表明2个配合物为同构结构,配合物中心均为七配位的畸变五角双锥结构。钴配合物2与CT-DNA的键合能力强于锰配合物1,两者与BSA的作用机理为静态淬灭机理,而键合常数值大小为1>2。在以H₂O₂作为诱导剂时,在同等条件下,2切割DNA的能力明显增强。通过加入自由基捕获剂证明了配合物对DNA的切割机理为氧化切割机理,其中活性氧为OH·。     

C,igahertz longitudinal acoustic phonons originating from ultrafast ligand field transitions in hematite thin films

The creation and propagation of longitudinal acoustic phonons （LAPs） in high quality hematite thin films （α-Fe203） epitaxially grown on different substrates （BaTiO3, SrTiO3, and LaAlO3） are investigated using the femtosecond pump- probe technique. Transient reflection measurements （AR/R） indicate the photo-excited electron dynamics, and the initial decay less than 1 ps and the slow decay of -500 ps are attributed to the electron-LO phonon coupling and electron-hole nonradiative recombination, respectively. LAPs in α-Fe2O3 film can be created by ultrafast excitation of the ligand field state, such as the ligand field transitions under 800-nm excitation as well as the ligand to metal charge-transfer with 400- nm excitation. The strain modulations of the sound velocity and the out-of-plane elastic properties are demonstrated in α-Fe2O3 film on different substrates.     

Overcoming Statistical Complexity: Selective Coordination of Three Different Metal Ions to a Ligand with Three Different Coordination Sites

In general, it is difficult to selectively introduce different metal ions at specific positions of a cluster‐like structure. This is mainly due to statistical problems as well as the reversibility of the formation of coordination bonds. To overcome this statistical problem, we used a carefully designed ligand, H₆L, which can accommodate three different kinds of metal ions in three types of coordination sites. The complex [LNiZn₂La]³⁺, which contains three different metals, was quantitatively obtained by a stepwise procedure, but different products were obtained when the metal ions were added in a different order. However, equilibration studies indicated that this complex was almost solely formed among 54 (=3×3×₃H₂) possible products upon heating; the formation efficiency (ca. 100 %) was significantly higher than the statistical probability (2.47 %). Such carefully designed ligands should be useful for the synthesis multimetallic systems, which are of interest because of the interplay between the different metals.     

氯化锌修饰蓝光量子点发光二极管EI北大核心CSCD

采用氯化锌(ZnCl_(2))修饰镉基CdSe/ZnS蓝光量子点(B-QD)薄膜,发现与量子点表面结合力更强的ZnCl_(2)能够部分取代量子点长链配体油酸,有效钝化量子点表面缺陷,提高薄膜的荧光量子效率(PLQY)。此外,由于ZnCl_(2)具有偶极作用,使量子点真空能级提高0.2 eV,一方面可改善电子和空穴载流子注入平衡,另一方面可有效降低发光器件的启亮电压,提高器件的发光寿命。这种无机配体修饰量子点薄膜的方法可能为解决蓝光量子点发光二极管(B-QLEDs)因空穴注入困难和量子点表面缺陷导致器件性能不高的问题提供一个有效思路。