3-((5-(3-吡啶基)-2-(1,3,4-噁二唑基))硫代)-2,4-戊二酮Cu(Ⅱ)/Zn(Ⅱ)/Mn(Ⅱ)配合物的合成及其晶体结构

将配体3-((5-(3-吡啶基)-2-(1,3,4-噁二唑基))硫代)-2,4-戊二酮(HL)与Cu(OAc)_2·H_2O、Zn(OAc)_2·2H_2O和Mn(OAc)_2·4H_2O分别进行配位反应,得到3个配位聚合物{[Cu_2(L)_4]·CHCl_3}_n(1)、{[Zn(L)_2]·4CHCl_3}_n(2)和{[Mn(L)_2]·4CHCl_3}_n(3),并通过元素分析、红外光谱、粉末X射线衍射、单晶X射线衍射等对配合物的结构进行了表征。在固体状态下,配位聚合物1形成1D螺旋链状结构,配位聚合物2和3形成2D网状结构。     

三维超分子锌/锰配合物的合成、晶体结构及理论计算

通过水热法合成了2个新的三维超分子配合物{[Zn_2(pzdc)(L)_2(H_2O)]·H_2O}_n(1)和[Mn(μ_2-O)(H_2O)_2(HL)]·NIPH(2)(H_2pzdc=吡嗪-2,3-二甲酸,H_2NIPH=5-硝基间苯二甲酸,HL=3-(2-吡啶基)吡唑))。并对其进行了元素分析、红外光谱、紫外光谱、热重、荧光光谱、X射线单晶和粉末衍射测定。配合物1是二维网状结构,配合物2为零维结构,这2个配合物通过氢键和π-π相互作用形成了三维超分子网状结构。此外,还用高斯09程序PBE0/LANL2DZ方法对配合物1和2进行了自然键轨道(NBO)分析,计算结果表明配位原子与Zn、Mn离子之间存在着共价作用。     

3-(2-吡啶基)-1,2,4-三唑配体Co(Ⅱ)Cu(Ⅱ)和Cd(Ⅱ)配合物的合成、结构及荧光性质（英文）

利用3-(2-吡啶基)-1,2,4-三唑配体(HL)和不同的金属盐设计合成了5个配合物[Co(HL)_2(H_2O)_2](NO_3)_2(1)、[Cu_2(L)_2(NO_3)_2(H_2O)_4](2)、 [Cu_2(L)_2(AcO)_2(H_2O)_2]·6H_2O(3)、[Cu_2(L)_2(HL)_2(ClO_4)_2]·2CH_3CN(4)和[Cd_2(L)_2(HL)_2(NO_3)_2]·2H_2O(5),并通过X射线单晶衍射、红外、元素分析、X射线粉末衍射和热重对配合物结构进行了表征。测试结果表明配合物1具有单核结构,并且可以通过氢键的相互作用形成二维超分子结构。配合物2~5为双核结构。配合物2和5可以通过氢键的相互作用形成二维超分子结构。配合物3通过氢键的相互作用形成三维超分子结构。研究了配合物中HL配体的配位模式。此外,研究了配体HL和配合物1和5的固态荧光性质及荧光寿命。     

水杨醛苯甲酰腙锰配合物的研究

水杨醛苯甲酰腙C_(14)H_(12)O_2N_2(H_2L)常作为三齿配体和金属离子配位,有两种不同配位形式:HL~-(只失去酚羟基质子)和L~(2-)(进一步失去胺基原子)。本文用以合成了下列两种不同价态锰的配合物:Mn(Ⅱ)(HL)_2和Mn(Ⅲ)(HL)L以及Mn(Ⅱ)(HL)(CH_3COO)·1.5H_2O和Mn(Ⅲ)L(CH_3COO)·0.5H_2O,迄今文献中只见Mn(Ⅱ)L和Mn(Ⅲ)LX(X=CH_3COO~-、Cl~-、Br~-)型双核锰配合物的研究报道。     

苯甲酰丙酮苯甲酰腙锰配合物的合成

以氧、氮为配位原子的锰配合物特别是多核配合物由于可作为多种锰蛋白活性部位的模型配合物研究,因此日益受到人们的关注。以β-二酮和芳酰肼形成的腙类化合物(H_2L)可作为三齿配体(ONO)以HL~-和L~(2-)的形式和过渡金属离子配位,但至今未见有关锰配合物的研究报导。本文利用由苯甲酰丙酮和苯甲酰肼缩合而形成的苯甲酰丙酮苯甲酰腙C_(17)H_(16)O_2N_2(H_2L)合成了锰(Ⅲ)配合物Mn(HL)L、Mn(HL)L·H_2O和Mn_2L_2(OCH_3)_2·2H_2O。     

以还原型钼磷酸盐[P_4Mo_6~vO_(28)(OH)_3]~(9-)为建筑单元构筑新型多维延展结构材料

向MoO_3,H_3PO_4和bpy(4,4'-bipyridine)组成的反应体系中分别引入Cd(OAc)_2·2H_2O和MnCl_2·4H_2O,在水热条件下合成了两种基于还原型钼磷酸盐[P_4Mo_6O_(28)(OH)_2]~(9-)(简称(P_4Mo_6})为建筑单元构筑的新型多维延展型无机-有机杂化材料(H_2bpy)_2[Cd(H_2O)]_3[Cd(HPO_4)_6(PO_4)_2(OH)_6(MoO_2)_(12)]·5H_2O(1)和(H_2bpy)_3[Mn(H_2O)_2]_2[Mn(HPO_4)_6(PO_4)_2(OH)_6(MoO_2)_(12)]·10H_2O(2),并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其进行了表征。结果表明,化合物1和2均属于三斜晶系,P1空间群。化合物1的阴离子|Cd(H_2O)]_3[Cd(HPO_4)_6(PO_4)_2(OH)_6(MoO_2)_(12)]~(2-)是由二聚体Cd[P_4Mo_6]_2通过{Cd_3}簇依次连接形成的一维无机链状结构;化合物2的阴离子[Mn(H_2O)_2]_2[Mn(HPO_4)_6(PO_4)_2(OH)_6(MoO_2)_(12)]~(3-)则是由二聚体Mn[P_4Mo_6]_2通过Mn~(2+)离子连接形成的二维无机层状结构。这2种无机延展结构均同质子化的bpy通过氢键作用形成不同的三维超分子网络。同时还探讨了化合物2的电化学性质。     

由吡啶-三羧酸配体构筑的锌(Ⅱ)和锰(Ⅱ)配合物的合成、晶体结构、荧光及磁性质

采用水热方法,用吡啶-三羧酸配体(H_3L)和2,2′-联咪唑(H_2biim 2,2′-biimidazole)、菲咯啉(phen)、2,2′-联吡啶(2,2′-bipy)分别与ZnCl_2和MnCl_2·4H_2O反应,合成了1个零维配合物[Zn(H_2biim)2(H_2O)_2][Zn(HL)(Hbiim)(H_2O)]_2·8H_2O(1)和2个具有一维链结构的配合物[Mn(μ-HL)(phen)(H_2O)]_n(2)、{[Mn(μ-HL)(2,2′-bipy)(H_2O)]·0.5(2,2′-bipy)}_n(3),并对其结构、荧光和磁性质进行了研究。结构分析结果表明3个配合物分别属于单斜晶系的P21/n和P21/c空间群。配合物1具有3个单核Zn单元组成的零维结构,这些单核单元通过O-H…O/N和N-H…O氢键作用进一步形成了三维超分子框架。配合物2和3具有一维链结构,而且这些链通过O-H…O氢键作用进一步形成了二维超分子网络。研究表明,配合物1在室温下能发出蓝色荧光,聚合物2中相邻Mn髤离子间存在反铁磁相互作用。     

Syntheses,Structures, and Properties of Two Cobalt(Ⅱ) Coordination Complexes Based on(Fluorene-9,9-diyl) dipropanoic Acid and 1,3-Bis(imidazol-1-yl)butane Ligands

Two new cobalt(II) coordination complexes, namely [Co(HL)_2(biim)(H_2O)_2]_n·n H_2O(1) and [Co(Et L)_2(biim)]_n·3 n(H_2O)·2 n(Et HL)(2)(H_2L =(fluorene-9,9-diyl)dipropanoic acid, biim = 1,3-bis(imidazol-1-yl)butane), have been synthesized using the same starting reactants but different solvent medium. The two complexes exhibit distinctly different structures. Compound 1 exhibits a one-dimensional linear chain structure. However, complex 2 reveals a one-dimensional zigzag chain structure. Thermogravimetric analyses(TGA) and luminescent properties of these two complexes have been discussed.     

1,2-环己二胺缩邻香兰素单核与四核镱稀土配合物的近红外性质（英文）

通过配体1,2-环己二胺缩邻香兰素(H2L)和不同的镱盐反应,合成了4个镱稀土配合物[Yb(H_2L)_2](ClO_4)_3·2CH_3OH·H_2O(1),[Yb_4(L)_4(NO_3)2(H_2O)_2](PF_6)_2·4CH_3CN(2),[Yb_4(L)_4(H_2O)_2Cl_2](PF6)_2·2CH_2Cl_2·2H_2O(3)和[Yb_4(L)_4(NO_3)_2(H2O)_2][Yb(NO_3)_3(H_2O)_2(CH_3OH)](NO_3)_2·4CH_2Cl_2·6CH_3OH(4)。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。     

基于4-甲基-3-苯基-5-(2-吡啶基)-1,2,4-三唑的Cu(Ⅱ)、Ni(Ⅱ)和Cd(Ⅱ)配合物的合成、晶体结构及性质（英文）

4-甲基-3-苯基-5-(2-吡啶基)-1,2,4-三唑(L)分别与CuCl_2·2H_2O、Ni(NO_3)_2·6H_2O、Cu(ClO_4)_2·6H_2O和Cd(NO_3)_2·4H_2O反应合成了配合物[CuL_2Cl]Cl·H_2O(1)、[NiL_2(H_2O)_2](NO_3)_2(2)、[CuL_2(H_2O)_2](ClO_4)_2(3)和[CdL_2(NO_3)_2]·CH_3CN(4),测定了它们的X射线单晶结构,并用红外光谱、紫外光谱、荧光和热重分析进行了表征。配合物1属于正交晶系,空间群为Fddd,中心离子Cu1(Ⅱ)具有畸变的四方锥构型[CuN_4Cl]。配合物2、3和4都属于单斜晶系,空间群分别为P2_1/n,P2_1/n和P2_1/c。配合物2、3和4的中心离子Ni1(Ⅱ)、Cu1(Ⅱ)和Cd1(Ⅱ)都为畸变的八面体构型[NiN_4O_2]、[CuN_4O_2]和[CdN_4O_2]。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.