羧酸铜与单螺旋吡啶胺配体自组装的两种新型超分子配合物

Two novel supramolecular complexes [Cu（bpapa）（dhbd）]·CHaOH （1） and [Cu（bpapa）（ma）]·ma （2） （bpapa= bis[6-（2-pyridylamino）pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=a-methacrylate） were rationally designed, synthesized and characterized by single crystal X-ray diffraction, IR, electronic spectroscopy and thermogravimetric analyses. Complex 1 was the first oligo-a-pyfidylamino complex based on hydroxypolycarboxylate and self-assembled into a 3D honeycomb configuration network with open channels and tubes containing 1D ladder-shaped double chains formed by hydrogen bonds and aromatic π-π stacking interactions. Complex 2 constructed a 2D supramolecular network extended by 1D chains from dimeric supramolecular synthon through noncovalent supramolecular interactions. In the two complexes, the chelating monohelical ligand adopted all-anti configuration. Density functional theory calculations were applied to 1 and 2.     

基于芳香四羧酸构筑的两种配位聚合物的荧光及磁性质（英文）

在溶剂热条件下,基于芳香四羧酸合成了2种新颖的配位聚合物:{[Zn2(tptc)(1,4-bimb)2]·H2O}n(1)和{[Ni(tptc)0.5(1,2-bimb)(H2O)]·H2O}n(2),其中,tptc为对-三联苯-3,3″,5,5″-四羧酸,1,4-bimb为1,4-二(咪唑-1-亚甲基)苯,1,2-bimb为1,2-二(咪唑-1-亚甲基)苯。结构分析表明,1为三维结构,拓扑符号为(86);2为二维层状网络,通过氢键相互作用进一步扩展为三维超分子结构。此外,我们还研究了1对阳离子、阴离子的荧光感应以及2的磁性质。     

Hydrothermal Synthesis and Structure of a New 3D Lanthanide—Carboxylate Framework,[La（btec）1／2（H2btec）1／2（H2O）]n（H4btec=1,2,4,5—Benzeneteracarboxylic acid）

The title complex, [La(btec)_1/2(H₂btec)_1/2 (H₂O)]_n (H₄btec= 1, 2,4,5‐benzenetetracarboxylic acid) (1) was synthesized by the hydrothermal reaction of 1,2,4,5‐benzenetetracarboxylic dianhydride with La(NO₃)₃·6H₂O in H₂O, and crystallizes in the triclinic system, space group P‐1 with a = 0.64403(3) nm, b = 0.94500(4) nm, c = 0.96380(5) nm, a = 88.535(2)°, β = 100.314(2)°, γ = 76.6470(10)°, V = 1.60968(10) nm³, Z = 2, and final R = 0.0274, R_w = 0.0735. In 1, each La(m) ion is coordinated by eight oxygen atoms from six carboxylate groups and one coordinated water molecule. Two different coordination modes of H₄btec were present in the structure, one of which contains two protonated carboxylate groups to balance the charge.     

A High－efficiency Preparation, Properties and Structure of （R, S ）－and （ S, S）－Pyrrolidine－2－carboxylic Acid 3,5－Dioxa－4－boracvclo.hepta [ 2,1－α; 3,4－α′] dinaphthalen－4－yl Esters

A highly-efficient preparative procedure for ( R, S )- and ( S, S)-pyrroHdine-2-carboxyHc acid 3,5-dioxa-4-boracyclohepta[2, 1-α ; 3,4-α′] dlnaphthalen-4-yl esters [ namely ( R, S )-BNBAP and (S, S )-BNBAP] is described and the crystal structure of (R, S )-BNBAP was obtained. The data indicate that ( R, S )-BNBAP is a spirocyclic inner borate salt with almost normal te-trahedral configuration. This structural form may be the basic reason for their high chemical, optical and thermodynamic sta-bility.     

Synthesis and electrochemical properties of 2,6-bis（6-aryl-[1,2,4]- triazolo[3,4-b][1,3,4]-thiadiazole-3-yl）pyridines

By the condensation of 2,6-bis（4-amino-5-mercapto-[1,2,4]-triazoles-2）pyridine with aromatic acid in the presence of phosphorus oxychloride. Compounds of 2,6-bis（6-aryl-[1,2,4]-triazolo[3,4-b][1,3,4]-thiadiazole-3-yl）pyridines were synthesized. Their structures were confirmed by IR, ^1H NMR spectroscopies and elemental analysis. Their electrochemical behavior and cyclic voltammogram also were be studied. The results showed that they have high ionization potentials and good affinity.     

钯催化的有机硼化物与羧酸衍生物的交叉偶联反应

钯催化的交叉偶联反应是构建C—C键的常用方法,近年来,钯催化的有机硼化物与羧酸衍生物的交叉偶联反应已成为偶联反应研究中的热点.本文综述了最近十几年多种有机硼化物与酰氯、酸酐、羧酸、氯甲酸衍生物、羧酸活性酯、羧酸硫酯的交叉偶联反应研究进展,并对该反应在有机合成中的应用进行了讨论.     

Coloring spectrophotometric determination of palladium ( Ⅱ ) with 4-( 5-chioro-2-pyridyl )-azo-1,3-diaminobenzene

研究了4-(5-氯-2-吡啶)-偶氮-1,3-二氨基苯(5-C1-PADAB)与Pd的显色反应,在0.48mol/LH3PO4介质和100℃水浴条件下,5-C1-PADAB与Pd(Ⅱ)反应生成2∶1稳定络合物,其最大吸收波长为570nm,表观摩尔吸光系数为6.39×104L·mol-1·cm-1.结果表明:Pd含量在0～1.2mg/L内符合比尔定律,方法已用于矿样中微量Pd的测定,结果与AAS法相符.样品分析结果的相对标准偏差小于4％,加标回收率为98.5％～103.0％.     

富羧酸基团的共轭微孔聚合物:结构单元对孔隙和气体吸附性能的影响

Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance. Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field. To address this fundamental issue, we used benzene, the simplest aromatic system, as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2). We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity, isosteric heat, gas adsorption, and gas selectivity. CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of 835 and 765 m²·g^-1, respectively, displaying high potential for carbon dioxide storage applications. CMP-COOH@1 and CMP-COOH@2 exhibited CO₂ capture capabilities of 2.17 and 2.63 mmol·g^-1 (at 273 K and 1.05 × 10⁵ Pa), respectively, which were higher than those of their counterpart polymers, CMP-1 and CMP-2, which showed CO₂ capture capabilities of 1.66 and 2.28 mmol·g^-1, respectively. Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity.     

硫杂吡啶番的合成和X射线结构分析

采用与文献不同的方法，在同一反应中同时得到了2，11-二硫[3．3]（3，5）吡啶番、2，11，20-三硫[3．3．3]（3，5）吡啶番和2,11，20，29-四硫[3．3．3．3]（3，5）吡啶番，通过^1H NMR、MS以及X射线晶体结构分析确定了其结构；丰富了吡啶番类化合物和与其形成配位化合物的结构和物性上的知识，为这些新型化合物的进一步研究提供了新的理论依据。     

氨基磺酸/浓硫酸协同催化合成羧酸乙酯

以肉桂酸和无水乙醇为原料、廉价的氨基磺酸/浓硫酸为协同催化剂、环己烷为带水剂,合成了肉桂乙酯,收率90.0%。反应的优化条件为:氨基磺酸/浓硫酸/肉桂酸/无水乙醇=1.9/1/9.1/31.8(物质的量之比),时间3 h。利用该优化条件,共合成了9种羧酸乙酯,包括芳香酸、脂肪酸、二元酸、不饱和酸的乙酯。该法突出的优点有:催化剂价廉易得且可重复使用、产率高、后处理简便。