基于柔性苯二乙酸构筑的三个钴配合物的晶体结构和电化学性质

利用水热法合成了3个钴配位聚合物{[Co_(1.5)(opda)_(1.5)(mbib)_2(H_2O)_2]·H_2O}_n(1),{[Co(mpda)(mbib)]·H_2O}_n(2)和{[Co(ppda)(mbib)]·H_2O}_n(3),并对其进行了元素分析、红外光谱、热重分析和X射线单晶衍射测定。结果表明这些配合物的不同结构主要是由于中心钴髤阳离子的配位几何结构、柔性苯二甲酸和双(咪唑)配体的配位方式和构象的不同。同时,还研究了3个钴配位聚合物的热稳定性和电化学性质。     

三维镍(Ⅱ)-镧(Ⅲ)混金属配位聚合物的合成、晶体结构及其荧光性质

以1,2,3-三氮唑基杂环多羧酸H_3ctia(H_3ctia=5-(4-carboxyl-1H-1,2,3-triazol-1-yl) isophthalic acid)为配体合成了一系列三维镍(Ⅱ)-镧(Ⅲ)混金属配位聚合物[Ln_2Ni(tia)_4(H_2O)_4]_n(Ln=La (1)、Ce (2)、Pr (3)、Nd (4)、Sm (5)、Eu (6)、Gd (7)、Tb (8)、Dy (9))和{[Yb_2Ni(tia)_4(H_2O)_2]·2H_2O}_n(10)(tia=5-(1H-1,2,3-triazol-1-yl)isophthalate)。X射线单晶衍射测试表明,配合物1~10皆具有三维网格结构,其中配合物1~9同构,而配合物10的组成与1~9一样,但晶体学结构则完全不同。在可见光区域,化合物5、6、8和9分别出现了Sm、Eu、Tb和Dy的特征发射峰,其中配合物6、8和9的荧光寿命分别为234、598和2.96μs;在近红外区域,配合物4、9和10分别出现了Nd、Dy和Yb的特征发射峰,对应的荧光寿命分别为4.25、3.42和5.66μs。     

两个基于柔性双苯并咪唑配体的锌配位聚合物的合成、晶体结构和荧光性质

以1,4-双(2-甲基苯并咪唑-1-亚甲基)苯(bmb)和2个芳香多羧酸1,2,4,5-均苯四酸(H4btec)、4-(3,4-二羧基苯甲酰)邻苯二甲酸(H4dcbp)为配体,在水热条件下合成了2个锌配位聚合物{[Zn(bmb)_(0.5)(btec)_(0.5)(H_2O)]·H_2O}_n(1)和{[Zn_2(bmb)_2(dcbp)]·5H_2O}_n(2),并用X射线单晶衍射、红外光谱、元素分析和粉末衍射对其结构进行了表征。晶体结构测试表明2个聚合物均为复杂的三维框架结构,配体bmb在2个配合物中均为μ_2-η~1∶η~1的配位模式。此外还研究了2个配合物的荧光性质和热稳定性。     

柔性配体构筑的三个构象多样的镧系羧酸配位聚合物:合成,结构和荧光性质（英文）

利用2,2'-(1,4-亚苯基)二(亚苯基)二(硫基)苯二羧酸(H_2L~1)和2,2'-(2,3,5,6-四甲基-1,4-亚苯基)二(亚甲基)二(硫基)苯二甲酸(H_2L~2)2个柔性二羧酸分別与镧系金属盐反应,通过溶剂热方法合成了3个配位聚合物:{[(NH_2(CH_3)_2[Nd(L~1)_2(DMF)]·2DMF}_n(1)和{[Ln(L~2)_(1.5)(H_2O)(DMF)_2]·2DMF}_n[Ln=Ce(2),Pr(3)]。利用元素分析、红外、粉末X射线衍射、热重分析等对配合物进行了表征。X射线单晶衍射分析表明:3个配合物均为二维的层状结构,并且2个配体在配合物中表现出不同的构象。(L~1)~(2-)在配合物1中表现出顺式和反式2种构象,(L~2)~(2-)在配合物2和3中仅表现出反式构象。此外,对配合物的热稳定性和荧光性质也进行了研究。     

稀土胺羧酸配合物的研究 Ⅱ.吡啶-2,6-二甲酸镧配合物的合成及其晶体结构

合成了吡啶-2,6-二甲酸稀土配合物晶体。元素分析表明,化学式为((CH_3)_4N)_2Ln(H_2DPA)_2(DPA)Cl(Ln为La、Ce,Pr、Nd和Sm;DPA为吡啶-2,6-二甲酸根)。用X射线衍射法测定了镧配合物的单晶结构,其结构式为((CH_3)_4N)_2[La(H_2DPA)_2(DPA)]Cl,属正交晶系,空间群Pccn。晶胞参数:α=1.0321(1),b=1.4951(2),c=2.0766(6)nm;V=3.2044(9)nm~3;Z=4。吡啶-2,6-二甲酸以三齿配位,镧的配位数为9,其配位多面体为扭曲的三冠三角棱柱体。     

基于柔性的高酞酸和双咪唑型配体的Ni(Ⅱ)/Cd(Ⅱ)/Zn(Ⅱ)配位聚合物的合成、结构和性质（英文）

基于柔性的高酞酸(H_2hmph)和双咪唑型配体,通过溶剂热法合成了3种新的配位聚合物:{[Ni_2(hmph)_2(bib)_2(H_2O)_2]·3H_2O}_n(1)、[Cd(hmph)(bib)]_n (2)和{[Zn(hmph)(bip)]·H_2O}_n (3),其中bib=1,4-双(1-咪唑基)苯、bip=3,5-双(1-咪唑基)吡啶。配合物1是由Ni-羧酸链之间通过bib配体桥联而成的二维单层结构;配合物2为Cd-羧酸双股链之间通过bib配体拓展而成的二维双层结构,并含有由羧基连接的双核单元;配合物3是由羧酸连接而成的双核Zn单元通过bip配体拓展形成的双股链。3个配合物都具有较高的热稳定性。磁性分析表明在配合物1中存在铁磁性交换偶合作用。另外,配合物2和3的荧光性质与相应的配体相比都表现出明显的蓝移。     

三个基于1,5-二(2-乙基苯并咪唑基)-戊烷柔性配体的镉配合物（英文）

通过设计柔性配体1,5-二(2-乙基苯并咪唑基)戊烷(bep),在二羧酸辅助配体的调控下成功制备了3个配位聚合物[Cd(bep)(sba)]_n(1),[Cd(bep)(bda)]_n(2),and{[Cd_2(bep)(ada)_2]·H_2O}_n(3)(H_2sba=4,4′-磺酰基二苯甲酸,H_2bda=4,4′-联苯二甲酸,H_2ada=1,3-金刚烷二乙酸)。配合物均呈现二维层状结构。配合物1由交替的Cd(Ⅱ)/bep/sba2-螺旋链构成。配合物2由Cd/bda2-单元构成二维结构,bep作为单齿配体与Cd(Ⅱ)配位。配合物3的二维层通过Cd/ada2-/H_2O氢键螺旋链拓展成三维超分子。此外,对配合物1~3的粉末X射线衍射、热稳定性以及荧光性质进行了研究。     

系列Ln(Ⅲ)配聚物的合成、结构及近红外发光性能

通过水热反应合成5种结构新颖的配聚物:{[Ln_2(1,3-bdc)_3(H_2O)_4](DMF(H_2O}_n[Ln=Pr(1),Nd(2),Gd(3)]和{[Ln_4(1,3-bdc)_6(H_2O)_4(DMF)](DMF(2H_2O}_n[Ln=Er(4),Ho(5)](1,3-bdc:间苯二甲酸,DMF:N,N-二甲基酰胺)。通过单晶X射线衍射、红外光谱、紫外-可见-近红外(UV-Vis-NIR)光谱、荧光光谱等技术手段对产物的结构和性能进行了表征。结果表明,配聚物1~3是同构的,属单斜晶系,P2(1)/n空间群;配聚物4、5是同构的,属三斜晶系,P-1空间群。在晶体中,间苯二甲酸根采用多样的配位模式,使配聚物呈现多维的结构。除配聚物4,其余均呈现Ln(Ⅲ)的特征NIR发光,并与其UV-Vis-NIR吸收光谱相关联。     

由2-(4'-羧基苯基)咪唑-4,5-二羧酸构筑的过渡金属配位聚合物的合成、结构及性质

在溶剂热条件下,由2-(4′-羧基苯基)咪唑-4,5-二羧酸(H_4L,C_(12)H_8N_2O_6),合成了4个配位聚合物{[M(H_3L)_2]·2H_2O}_n(M=Zn(1),Cd(2),Co(3)),[Cd(H_2L)(H_2O)]_n(4)。用元素分析、红外光谱、热重分析和单晶X射线衍射对配合物进行了表征和结构分析。结构分析结果表明:1～3是异质同晶。配体失去1个质子以H_3L~-的形式通过单齿和N,O-双齿螯合的配位模式与中心金属离子配位,构成一个略有变形的八面体结构。对于配合物4来说,配体失去2个质子以H_2L~(2-)的形式分别通过单齿和N,O-双齿螯合的配位方式与Cd~(2+)配位,中心离子采取扭曲的七配位五角双锥配位模式,并且通过配体苯环上羧基氧原子的双齿桥联作用连接2个中心离子,形成四元环的双核结构;同时呈现双节点(3,6)-连接的二维拓扑网络(4.4.4)(4.4.4.4.4.4.5.6.6.6.6.6)。测定了产物的固体荧光光谱;用EtBr荧光探针法研究了配体及配合物与ct-DNA的相互作用。     

3—磺基—4—羟基香豆素希土化合物的合成及性质

在不同条件下制得三种类型的希土与3-磺基-4-羟基香豆素(H_2SHC)化合物,元素分析确定了它们的组成分别为Ln(HSHC)_3·9H_2(Ln=La,Pr,Nd,Gd,Dy,Er,Yb,Y),Ln_2(SHC)_3.nH_2O(Ln:La,Pr,Nd,Sm,Gd,N:4或6)和Na,Ln(3HC),·H:O(Ln:Er,Yb).并通过它们的摩尔电导戌\重,溶解度,红外光谱和电子吸收光谱对各种化合物进行了结构和性质的研究。     

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%.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.