三个低维Zn^Ⅱ-二膦酸配位聚合物的合成、结构及荧光性能研究

通过引入第二配体2,2′-联吡啶（2,2′-bipyridine,bipy）,在水热条件下得到3个低维ZnⅡ-二膦酸配位聚合物：[Zn1.5（H2L）（bipy）（H2O）]·3H2O（1）,[Zn（H3L）（bipy）]2（2）,[Zn（H3L）（bipy）（H2O）]·H2O（3）（H5L=1-羟亚乙基-1,1-二膦酸,CH3C（OH）（PO3H2）2）。采用单晶X-射线衍射、粉末X-射线衍射（PXRD）、红外光谱（IR）、元素分析、热重（TG-DSC）等测试手段对产物的结构进行了表征。单晶X-射线衍射数据分析表明化合物1为一维梯形双链结构,结构中含有2个晶体学独立的锌离子,分别以四配位和六配位模式与配体连接。化合物2为O-P-O双桥连接三角双锥[ZnO3N2]而成的双核零维结构。化合物3为八面体[ZnO4N2]通过O-P-O单桥连接而成的一维链状结构。氢键和π-π堆积作用进一步将3个低维ZnⅡ-二膦酸化合物扩展为三维超分子。对化合物1~3进行荧光性能的研究,测试结果表明,3个化合物均发射出强度远大于配体bipy的荧光发射峰（λem=374nm（1）、388nm（2）、387nm（3）,λex=252nm）,该峰来源于第二配体bipy（λem=391nm,λex=252nm）分子内部的π＊-π电荷转移。电化学测试结果显示3个化合物均表现出一步单电子氧化还原过程,与自由配体相比给电子能力增强,未来可作为空穴传输材料在光电领域得到应用。

多酸配位聚合物的制备与表征——推荐一个综合化学实验

介绍了一个综合化学新实验--多酸配位聚合物的制备与表征。通过杂多酸和有机配体的合成、多酸配位聚合物的制备和性能表征,使学生了解多酸配位聚合物这一无机合成化学前沿领域,在引导学生进行材料合成及性质表征的过程中,提高学生对已学知识融会贯通的能力,提升学生学习化学的兴趣。本实验综合了无机、有机化学知识点以及实验、仪器操作和数据分析能力的培养,可纳入高年级综合化学实验。

二维钡钨双金属膦酸配位聚合物的合成、结构及荧光研究

水热条件下,以2,2'-联吡啶(2,2'-bipy)为结构导向剂,利用Ba(II)盐,硅钨酸与1-羟基-2-(3-吡啶基)亚乙基-1,1-二膦酸(H5L=(H4C5N)CH2C(OH)(PO3H2)2)反应,得到二维钡钨双金属膦酸配位聚合物{[Ba2(L-H)(H2O)2(WO3)]·H2O}n(化合物1).该化合物为单斜晶系,C2/c空间群,晶胞参数:a=2.305(2)nm,b=0.7310(5)nm,c=2.033(1)nm,β=93.160(7)°,V=3.420(4)nm3,Z=8,R1=0.0293,ωR2=0.0702.单晶X-射线衍射分析表明其具有二维双金属无机层状结构.荧光测试结果表明,在236nm发射波长下,出现2个来自于膦酸分子内(λem=380.5nm,437.5nm)π*-π跃迁的荧光发射峰:λem=317nm,445.5nm.

自组装形成的透明质酸-铜-槲皮素配位聚合物纳米粒子对乳腺癌的协同治疗作用

目的:探讨自组装形成的具有协同治疗作用的透明质酸-铜-槲皮素配位聚合物纳米粒子(HCQ NP)对乳腺癌的协同治疗作用。方法:采用自组装方法合成HCQ NP,并通过透射电镜、动态光散射、红外光谱分析和电感耦合等离子体质谱对其进行表征;采用亚甲蓝紫外吸收法测定HCQ NP与不同浓度的过氧化氢(H_(2)O_(2))反应生成羟基自由基(·OH)的能力;在模拟肿瘤微环境下,采用CCK-8法分别评价不同浓度的HCQ NP对乳腺癌MDA-MB-231细胞的抑制效果。结果:自组装形成的HCQ NP具有形状类似球形、大小均一的特点,并对乳腺癌MDA-MB-231细胞具有显著的协同抑制作用。结论:自组装形成的HCQ NP对乳腺癌MDA-MB-231细胞具有协同抑制作用。

多酸化学综合性实验:Dawson型多酸配位聚合物制备与表征

设计了Dawson型杂多酸的制备实验,同时结合最新科研成果,引入配体和过渡金属离子与Dawson型杂多酸水热合成多酸配位聚合物,并通过X射线粉末衍射表征、红外和热重对多酸配位聚合物进行结构表征。通过该实验,不仅让学生了解多酸配位聚合物这一无机合成化学前沿领域,还可以锻炼学生的科研思维,在培养化学研究兴趣的同时提升创新思维和知识融会贯通的能力。

Syntheses and catalytic performances of three coordination polymers with tetracarboxylate ligands

Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.

Syntheses,crystal structures,and catalytic properties of three zinc(Ⅱ),cobalt(Ⅱ)and nickel(Ⅱ)coordination polymers constructed from 5⁃(4⁃carboxyphenoxy)nicotinic acid

Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.

一种含钴POMCPs@Ti_(3)C_(2)T_(x)超级电容器负极材料的制备及性能

介绍了一种超级电容器负极材料.采用简便的一步水热法成功合成了一种多金属氧酸盐配位聚合物(POMCP1),并通过三电极系统测试其超级电容器性能.在电流密度为8 A·g^(-1)时,比电容达到了186.3 F·g^(-1);在电流密度为30 A·g^(-1)时,其比电容仍然维持在123.9 F·g^(-1).并将POMCP1与具有优异导电性的MXene材料Ti_(3)C_(2)T_(x)结合,由此产生的杂化材料称为POMCP1@Ti_(3)C_(2)T_(x).POMCP1@Ti_(3)C_(2)T_(x)表现出优异的比电容,在电流密度为8 A·g^(-1)时,比电容为521.7 F·g^(-1);在电流密度为30 A·g^(-1)时,其比电容仍然维持在402.8 F·g^(-1),表现出优秀的倍率性能,超过了该类别中许多其他材料,为开发基于多酸基配位聚合物作为超级电容的杂化电极材料提供了一种有效的途径.

Chiral fluorescent sensor Tb^(3+)@Cd‑CP based on camphoric acid for the enantioselective recognition of R‑and S‑propylene glycol

Herein,a layered chiral coordination polymer,[Cd2(D‑cam)_(2)(2,2′‑bipy)_(2)]_(n)(Cd‑CP),was synthesized using a solvothermal method with camphoric acid(D‑H_(2)cam),2,2′‑bipyridine(2,2′‑bipy)and Cd^(2+),and Tb^(3+)@Cd‑CP was in‑situ synthesized introducing Tb^(3+)ions.The fluorescence experiments revealed that compared to Cd‑CP,Tb^(3+)@Cd‑CP exhibited ultra‑high fluorescence performance.The luminescence sensing performance demonstrated that Tb^(3+)@Cd‑CP could distinguish R/S‑propylene glycol(R/S‑PG)by fluorescence responses,with fluorescence quenching constant of 5.3×10^(3)and 2.0×10^(3)L·mol^(-1)respectively and the enantioselectivity factor(α)of 2.65.Moreover,Tb^(3+)@Cd‑CP demonstrated limits of detection of 9.3 and 19.0μmol·L^(-1)for R‑PG and S‑PG,respectively,and showed good reproducibility.

层状铀酰膦酸配位聚合物作为双响应光致发光温度计

具有光致发光性质的铀酰膦酸配位聚合物已经用于温度传感,但尚未用于双响应发光温度计.本工作报道了一种基于邻羧基苯甲基膦酸配体(2-pmbH_(3))的层状铀酰膦酸配位聚合物,即(α-C_(8)H_(12)N)[UO_(2)(2-pmb)](1).其中铀酰离子通过2-pmb^(3−)配体连接成层,外消旋且质子化的苯乙胺分子作为抗衡离子占据层间.层内最近的U1···U1距离为0.541 nm.化合物1表现出较高的热稳定性和水稳定性.光致发光性质表明,化合物1在室温下发出绿光,可以在200~360 K的温度范围内作为发光强度和寿命的双响应发光温度计,其强度依赖的最大灵敏度为2.96%·K^(−1)(330 K),寿命依赖的最大灵敏度为2.51%·K^(−1)(350 K),实现了工作温度更高、灵敏度更高的铀酰基温度计.相对论密度泛函(DFT)计算证实了该化合物的稳定性来源于铀酰赤道面膦酸氧2p轨道与铀5fφ轨道相互作用.计算表明,在320 nm和412 nm附近的两个峰为O=U=O内氧以及膦酸氧2p到铀5f_(δ)(f_(z(x2−y2)))的配体到金属电荷转移(LMCT).

Transition metal coordination polymers with flexible dicarboxylate ligand:Synthesis,characterization,and photoluminescence property

Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.

冀东油田浅层调剖用有机铬交联剂的开发

开发采用有机铬交联体系为Cr^(3+)/丙酸络合物,解决了Cr^(6+)的环保问题,该体系适应性强,且相对成本低,胶体强度高,成胶热稳时间较长,但存在成胶速度快不易控制的问题,影响体系注入、波及效果。这一基础上,加入一定的延缓剂使得丙酸铬离子交联剂制得的弱凝胶成胶稳定时间更长、强度范围更广、实用性、注入性更强,解决目前存在的成胶速度过快、地面粘度大的问题。

表面、界面的作用与粘接机理(二)

介绍了材料粘接过程界面区的酸碱作用与化学反应对粘接性能的贡献,其内容包括氢键力的作用,酸碱配位作用的考查,酸碱作用对粘接性能的影响和界面化学结合的形成途径及其对粘接性能的影响。

甲醇转化制丙烯反应机理

以杂化轨道理论和关于含Si、Al元素催化剂酸中心的认识为理论依据和研究方法,从反应物与催化剂B酸中心相互作用为切入点,分析相互作用过程中甲醇与B酸中心分子结构变化,揭示甲醇制烯烃反应机理本质。研究结果表明甲醇转化制丙烯反应过程可分为3步:(1)B酸中心释放H +攻击甲醇分子中C-O键,C-O键断裂生成甲基碳正离子(CH + 3)和H 2O,CH + 3中C原子外层有个空轨道,释放了H +后的B酸中心失去活性。(2)失活B酸中心从CH + 3中获得H +,反应生成了一种新中间体H-form,H-form中C原子外层有1对孤对电子(e -)和1个空轨道,结构式为C ↑↓〇 H 2;失活的B酸中心获得H +后恢复活性。第3步,有3个H-form结构的C原子,第1个C原子上的孤对e -占据第2个C原子上空轨道,第2个C原子上的孤对e -占据第1个C原子上空轨道,彼此共用2对e -,形成C=C键;第3个C原子上的空轨道与第1个C原子上C、H原子重叠轨道再次重叠,形成C、H和C三原子共用1对e -结构,结果是第1个C原子与第2个C原子形成C=C键,第1个C原子与第3个C原子形成C-C键,3个C原子形成C=C-C结构,即生成丙烯。

甲醇制丁烯反应机理研究

以杂化轨道理论和关于含Si、Al元素催化剂酸中心的认识为理论依据和研究方法,从反应物与催化剂B酸中心相互作用为切入点,分析相互作用过程中甲醇与B酸中心分子结构变化,揭示甲醇制烯烃反应机理本质。结果发现,中间体H-formC↑↓〇H2结构中碳原子外层有1对孤对电子和1个空轨道,是构成不同碳数、不同结构烯烃分子的基本结构单元。甲醇在B酸中心作用下反应生成丁烯分3步:(1)B酸中心释放出H+攻击甲醇分子C-O键,C-O键断裂生成甲基碳正离子CH3+和H2O,B酸中心失去活性;(2)失活B酸中心从CH3+获得H+恢复活性,CH3+反应生成中间体H-formC↑↓〇H2;(3)C↑↓〇H2是构成烯烃的基本结构单元,4个C↑↓OH2可以生成不同结构丁烯分子。

甲醇制乙烯和二甲醚反应机理研讨

以杂化轨道理论和关于含Si、Al元素催化剂酸中心认识为理论依据和研究方法,以甲醇分子中C、H原子与催化剂B酸中心中Al原子相互作用为切入点,分析催化剂B酸中心中Al原子外层电子轨道变化与甲醇分子中C原子外层电子轨道变化间的相互关系,探讨甲醇制乙烯、二甲醚的反应机理。结果发现:中间体H-form C↑↓〇H2是构成乙烯、二甲醚的基本结构单元;甲醇制乙烯、二甲醚反应机理分3步:(1)B酸中心释放H+攻击甲醇分子中C-O键,C-O键断裂生成甲基碳正离子(CH3+),B酸中心失去活性;(2)失活B酸中心从CH3+中获得H+恢复活性,CH3+失去H+生成中间体C↑↓〇H2;(3)2个中间体C↑↓〇H2结合生成乙烯和二甲醚。

Solid-state Synthesis at Low-heating Temperature and Crystal Structure of a Dinuclear Molybdenum Complex with Oxalate Ligand[Bu_4N]_2[Mo_2O_2(OH)_2Cl_4(C_2O_4)]

The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.

Redox behavior and chemical species of arsenic in acidic aqueous system

Arsenic(As)removal from smelting acidic wastewater is an urgent task.The most common method is oxidation of trivalent As(III)to pentavalent As(V)subsequently precipitated by ferric(Fe(III))salts.Foundations of redox behavior and chemical species are of great importance for understanding As removal.In this work,cyclic voltammetry(CV)and UV?Vis spectroscopy were used for laboratory observation;meanwhile HSC and MINTEQ software were employed for theoretical analyses.It is found that As(III)oxidation,a multiple electron transfer reaction,is diffusion-controlled.The oxidation over-potential is very high(about0.9V)in sulfuric acid solutions(pH1.0).In addition,Fe(III)?As(V)complexes are evidenced by UV?Vis spectra and chemical species analyses in series of Fe(III)?As(V)?H2SO4?H2O solutions.Therefore,the Fe(III)and As(V)species distribution against pH values are determined and a newφ?pH diagram with inclusion of Fe?As complexes is consequently compiled based on thermodynamic data predicted by other researchers.

XAFS Study of Coordination Structure of Cu（L-His）2 in Solution

Multiple coordination modes are present copper coordination environment varies in the CuII-histidine complex in solution and the with pH. In this work, we have investigated the coordination geometry of Cu（His）2 complex using X-ray absorption fine structure （XAFS） analysis. Copper K-edge XAFS spectra were acquired on aqueous Cu2＋ samples with his- tidine at different pH values. The coordination environments were further confirmed by chemically modified histidine. Results show that the caboxylate groups coordinate at acidic condition, while amino and imidazole nitrogens get coordinated at higher pH. For the co- ordination geometry of Cu（His）2 in solution at physiological pH, the sixfold coordination is preferentially formed, while the fivefold coordination can co-exist in equilibrium.

甲醇与一氧化碳制芳烃反应机理

甲醇与一氧化碳(CO)反应制芳烃是煤制芳烃技术重大突破。以杂化轨道理论和对含Si、Al元素催化剂酸中心认识为理论依据和研究方法,以反应物分子与催化剂B酸中心相互作用为切入点,分析其相互作用,揭示甲醇与CO制芳烃反应机理。结果发现:甲醇与CO制芳烃反应过程分为5步:(1)B酸中心释放H+攻击甲醇分子中C-O键,C-O键断裂生成甲基碳正离子(CH3^+),B酸中心失活;(2)失活B酸中心从CH3^+获得H+,反应生成中间体C↑↓〇H2,C↑↓〇H2中C原子外层有1对孤对电子(e-)和1个空轨道,失活的B酸中心获得H+后恢复活性;(3)C↑↓〇H2与CO反应生成中间体C↑↓↑〇H和C↑,↑↑H;(4)6个C↑↓↑〇H或6个C↑,↑↑H可以形成苯环结构,但构成方式不同;(5)C↑↓〇H2与苯环反应生成混合芳烃。