1，1'-二羟基-5，5'-联四唑的镧系金属配合物的合成、表征及热行为

以1,1′-二羟基-5,5′-联四唑(H_2BTO)为配体,镧系金属离子作为金属中心,采用溶剂热法制备了5种金属配合物:[La_2(BTO)_3(H_2O)_8]·2H_2O (1)、[Ce_2(BTO)_3(H_2O)_8]·2H_2O (2)、[Pr_2(BTO)_3(H_2O)_8]·2H_2O (3)、[Sm_2(BTO)_3(H_2O)_8]·2H_2O (4)和[Nd_2(BTO)_3(DMF)_4]·6H_2O (5)。通过单晶X射线衍射和元素分析对5种配合物的结构进行了表征。结果表明,5种配合物均属于单斜晶系,P2_1/n空间群。利用差示扫描量热法研究了配合物1～4的热稳定性,采用Kissinger法和Ozawa法分别计算了其热分解动力学参数。     

New Heterocyclic Phosphorus Ylides: Synthesis,Crystal Structure,and Theoretical Calculation of Alkyl Substituted 3-(4-Benzoyl-1,5-diphenyl-2,3-dihydro-1H-pyrazol-3-yl)-3-oxo-2-(triphenylphosphoranylidene) Propanoates

Novel alkyl substituted 3-(4-benzoyl-1,5-diphenyl-2,3-dihydro-1H-pyrazol-3-yl)-3-oxo-2-(triphenylphosphoranylidene) propanoates (3) were synthesized from 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-carbonylchloride (1) and alkyl (triphenylphosphoranylidene) acetates (2a–b). The synthesized compounds were characterized by elemental analysis, spectroscopic studies (3a–b), and single crystal X-ray diffraction (3a). The mechanism of the reaction between (1) and (2a) was studied by AM1, and the geometrical parameters of the studied molecules were also carried out in B3LYP methods with the standard 6–31G (d,p) basis set. NBO analysis were studied for 1 and 2a B3LYP methods with the standard 6–31G (d,p) basis set.     

由2-甲基-4-噻唑甲酸构筑的过渡金属配合物的合成、晶体结构及与DNA作用

以2-甲基-4-噻唑甲酸（HMTZA,C₅H₅NO₂S）为配体合成了3种新型过渡金属配合物[Co（MTZA）₂（H₂O）₂]·3H₂O（1）,[Cu（MTZA）₂（H₂O）]·2H₂O（2）和[Zn（MTZA）₂（H₂O）₂]·3H₂O（3）。对配合物进行了元素分析、红外光谱和热重分析表征,用单晶X射线衍射方法测定了配合物的晶体结构。结果表明,配合物1属于单斜晶系,空间群为P2₁/n,中心金属Co（Ⅱ）离子的配位数为6,配位构型为略为变形的八面体;配合物2属于三斜晶系,空间群为P1,Cu（Ⅱ）离子的配位构型是一个畸变的四方锥;配合物3属单斜晶系,空间群为P2₁/n,中心金属Zn（Ⅱ）离子的配位构型为畸变的八面体。用溴化乙锭荧光探针法测定了配体和配合物与DNA作用的荧光光谱,结果显示无论配体还是配合物均能使EB-DNA复合体系发生不同程度的荧光猝灭,且配合物的作用强度远大于配体。     

Solid and solution states studies of two Mn(II) complexes based on N-oxidized pyridine-2,5-dicarboxylic acid

Abstract

Two coordination complexes, [Mn₂(pydco)₂(phen)₂(H₂O)₂]·2H₂O (1) and [Mn(3-pyco)₂(H₂O)₄] (2), based on Mn(II), pyridine-2,5-dicarboxylic acid N-oxide (H₂pydco), and 1,10-phenanthroline (phen) as organic ligands have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X-ray diffraction. We have synthesized the first Mn(II) complex of H₂pydco. Interestingly, in situ hydrothermal decarboxylation occurred in 2 and (pydco)^2– was totally transformed into pyridine-3-carboxylate N-oxide (3-pyco)^– under hydrothermal conditions. The complexation reactions of these molecules with Mn²⁺ ions were investigated by means of solution studies. The stoichiometry of the most abundant species in the solution (prior to the pH at which precipitation occurs) was very close to that of the corresponding crystalline solid-state complexes.     

Pb(II) and Bi(III) complexes involving a Schiff base ligand: syntheses,structures, physical,and antioxidant properties

Two new complexes, {[PbL(NO₃)₂H₂O]H₂O}_n (1) and [BiL₂(NO₃)₂]NO₃ (2), based on (E)-3-chloro-6-[2-(pyrazin-2-ylmethylene)hydrazinyl]pyridazine (L) were synthesized and characterized by IR spectra, single-crystal X-ray diffraction, and elemental analyzes. X-ray single crystal diffraction experiments of 1 and 2 display that extensive hydrogen bonds and π…π stacking interactions construct the 1-D infinite chain {[PbL(NO₃)₂H₂O]H₂O}_n and [BiL₂(NO₃)₂]NO₃ into two 3-D supramolecular frameworks. Interestingly, pure phase PbO nano-particles were synthesized by thermolysis of 1 and characterized by scanning electron microscopy and X-ray powder diffraction analyzes. Furthermore, antioxidant activities of L, 1, and 2 were also studied.     

基于2，3，5，6-四氟对苯二甲酸构筑的两个超分子网络结构的合成、结构和荧光性质

在水热条件下合成了基于四氟对苯二甲酸的2个二维微孔配位聚合物{[Cd₂（IP）₂（tfBDC）₂（H₂O）₂]·H₂O}_n（1）和{[Mn₂（IP）₂（tfBDC）₂（H₂O）₂]·H₂O}_n（2）（tfBDC=2,3,5,6-四氟对苯二甲酸,IP=1-H-咪唑[4,5-f][1,10]-菲咯啉）。二维层状结构是4⁴-网状结构,三维超分子结构是由氢键连接相邻的二维层状结构而形成的。2个配位聚合物均用元素分析、热重分析（TGA）、粉末衍射（PXRD）、红外光谱（FT-IR）进行了表征,且对配合物1的荧光性质进行了详细的分析。     

Dicationic liquid mediated synthesis of tetrazoloquinolinyl methoxy phenyl 4-thiazolidinones and their antibacterial and antitubercular evaluation

In a search of new potentially active antitubercular agents here we have synthesized 3-substituted phenyl-2-(4-(tetrazolo[1,5-a]quinolin-4-ylmethoxy)phenyl)thiazolidin-4-ones (8a–l) and evaluated their antibacterial, particularly antitubercular activity. These have been conveniently synthesized by performing one–pot cyclocondensation of 4-(tetrazolo[1,5-a]quinolin-4-ylmethoxy)benzaldehyde, anilines and mercaptoacetic acid in dicationic ionic liquid, (3-methyl-1-[3-(methyl-1H-imidazolium-1-yl)propyl]-1H-imidazolium dibromide [C₃(MIM)₂–2Br]) and obtained excellent yields of (8a–l). 4-Thiazolidinones (8a–l) were thoroughly characterized by their spectral analyses. These compounds have been screened for their in vitro antitubercular activity against Mycobacterium tuberculosis H37Ra and Mycobacterium bovis (BCG). The compounds 8a, 8c, and 8e exhibited notable in vitro antitubercular activity compare to the reference, Rifampicin. Molecular docking study has also been performed to know the binding mode of these analogs in to the active site of DprE1 enzyme. The synthesized compounds were also evaluated for their in vitro antibacterial activity and amongst them compound 8k has shown moderate activity against both gram-negative and gram-positive bacterial strains.     

基于2，5-二溴对苯二羧酸配体的镧系金属有机骨架的合成、结构及性质

采用溶剂热法,以2,5-二溴对苯二甲酸(H₂L)为配体,分别与六水合硝酸钕、六水合硝酸钆反应合成了2种镧系金属有机骨架(MOFs)：{[Nd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (1)和{[Gd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (2)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、荧光光谱、热重分析等测试方法对其进行了结构表征与性质研究。结果表明,2个配合物均是以稀土离子为金属节点,与配体相互连接,形成无限延伸的三维网状结构。     

基于2,5-二溴对苯二羧酸配体的镧系金属有机骨架的合成、结构及性质

采用溶剂热法, 以2, 5-二溴对苯二甲酸(H₂L)为配体, 分别与六水合硝酸钕、六水合硝酸钆反应合成了 2种镧系金属有机骨架(MOFs):{[Nd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (1)和{[Gd₂(L)₃(DMF)₂(H₂O)₂]·2DMF}_n (2)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、荧光光谱、热重分析等测试方法对其进行了结构表征与性质研究。结果表明, 2个配合物均是以稀土离子为金属节点, 与配体相互连接, 形成无限延伸的三维网状结构。     

Two 3-D metal-organic frameworks constructed by 2-methyl or 2-ethyl imidazole dicarboxylates

Two polymeric frameworks, [Zn₅(MIDC)₂(HMIDC)₂(phen)₅] _n (1) (H₃MIDC?=?2-methyl-1H-imidazole-4,5-dicarboxylic acid, phen?=?1,10-phenanthroline) and {[Ca₂(HEIDC)₂(H₂O)]?·?H₂O} _n (2) (H₃EIDC?=?2-ethyl-1H-imidazole-4,5-dicarboxylic acid), have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Compound 1 exhibits a 3-D structure constructed from 2-D layer motifs joined by µ ₂-HMIDC^2? or µ ₃-MIDC^3? ligands. Compound 2 also presents a 3-D framework, generated from 1-D chains linked by HEIDC^2? ligands by two different µ₅-modes. The thermal and solid-state photoluminescence properties of both the complexes have been determined.     

Synthesis,structures and photoluminescence of two Er(III) coordination polymers

Two new erbium compounds, [Er₂(BDC)₃(DMF)₂] (1) and [Er₂(CQC)₃(DMF)₃(H₂O)]?·?DMF?·?H₂O (2), where BDC stands for 1,4-benzenedicarboxylate, CQC for 2-(4-carboxyquinolin-2-yl)quinoline-4-carboxylate, and DMF for N,N-dimethylformamide, have been synthesized through pre-heating and cooling-down crystallization. In 1 the Er(III) is seven-coordinate with oxygen atoms from six BDC and one DMF, forming a three-dimensional open-framework structure. Compound 2 possesses a 2D structure based on dinuclear Er(III) building units. The photoluminescence of 1 has also been investigated.     

Synthesis and characterization of two 3-D polymeric lanthanide complexes constructed from 1,2,4,5-benzenetetracarboxylic acid

Two 3-D porous coordination polymers, [Nd(^abtec)_2/4(^bbtec)_2/4(H₂O)] _n (1) and [NdYb(^cbtec)_2/4(^dbtec)_2/4(^ebtec)_2/4(H₂O)₄] _n (2), have been prepared by the hydrothermal method at 160°C. Both complexes were characterized by elemental analyses, photoluminescence spectra, and single-crystal X-ray diffraction.     

Synthesis,spectroscopic (IR,electronic, FAB-mass,and PXRD), magnetic,and antimicrobial studies of new iron(III) complexes containing Schiff bases and substituted benzoxazole ligands

Mixed ligand complexes of iron(III), [Fe(sb)₂(py)Cl]?·?2H₂O (1–9) [where sbH?=?Schiff bases (derived from condensation of 2-aminopyridine (sapH), 2-aminophenol (saphH), o-toluidine (o-smabH), aminobenzene (sabH), p-toluidine (p-smabH), 3-nitroaniline (snabH), and anthranilic acid (saaH) with salicylaldehyde and substituted (mercapto-)benzimidazole (mbzH), {2-(o-hydroxyphenyl)}benzoxazole, (pboxH)], have been synthesized by the interactions of iron(III) chloride with corresponding ligands in 1?:?2 molar ratio in refluxing pyridine. These complexes have been characterized by elemental analyses, melting points, spectral, and magnetic studies. Powder X-ray diffraction studies of some representative complexes are also reported herein. The antibacterial and antifungal activities of the free ligands and their iron(III) complexes were found in vitro. The complexes showed good antibacterial and antifungal effect to some bacteria and fungi. Two standard antibiotics (chloromphenicol and terbinafine) were used for comparison with these complexes.     

由4-甲基-1,2,3-噻二唑-5-甲酸构筑的铜配合物的合成、晶体结构及与DNA作用

由4-甲基-1,2,3-噻二唑-5-甲酸（HMTC,C₄H₄N₂O₂S）和菲咯啉（Phen）合成了2个铜配合物[Cu（MTC）₂（H₂O）₂]_n （1）,[Cu₂（MTC）₂（Phen）₂（H₂O）₄]（MTC）₂ （2）。用元素分析、红外光谱、热重分析、粉末X射线衍射进行表征,用单晶X射线衍射方法测定了配合物的晶体结构。结果表明,配合物1是一维链状结构,属于单斜晶系P2₁/c空间群,中心金属铜（Ⅱ）离子的配位构型是一个畸变的四方锥结构。配合物2属于三斜晶系,P1空间群,是一个双核结构,由2个配位水分子上的氧桥连2个铜（Ⅱ）离子形成六配位的扭曲八面体结构。用溴化乙锭荧光探针测定了配体和配合物与DNA的相互作用,结果显示无论是配体还是配合物均能使EB-DNA复合体系的荧光发生不同程度的猝灭,且配合物的作用强度大于配体,具有刚性平面辅助配体的配合物2的作用强度又大于不加辅助配体的配合物1。     

由4-甲基-1,2,3-噻二唑-5-甲酸构筑的铜配合物的合成、晶体结构及与DNA作用

由4-甲基-1,2,3-噻二唑-5-甲酸(HMTC,C₄H₄N₂O₂S)和菲咯啉(Phen)合成了2个铜配合物[Cu(MTC)2(H₂O)₂]_n(1),[Cu₂(MTC)₂(Phen)₂(H₂O)₄](MTC)₂(2)。用元素分析、红外光谱、热重分析、粉末X射线衍射进行表征,用单晶X射线衍射方法测定了配合物的晶体结构。结果表明,配合物1是一维链状结构,属于单斜晶系,P21/c空间群,中心金属铜(Ⅱ)离子的配位构型是一个畸变的四方锥结构。配合物2属于三斜晶系,P1空间群,是一个双核结构,由2个配位水分子上的氧桥连2个铜(Ⅱ)离子形成六配位的扭曲八面体结构。用溴化乙锭荧光探针测定了配体和配合物与DNA的相互作用,结果显示无论是配体还是配合物均能使EB-DNA复合体系的荧光发生不同程度的猝灭,且配合物的作用强度大于配体,具有刚性平面辅助配体的配合物2的作用强度又大于不加辅助配体的配合物1。     

4, 4'-二(1-咪唑基)苯硫醚及邻苯二甲酸构筑的两个配位聚合物的合成、晶体结构及荧光性质

在温和的水热条件下,以4,4'-二(1-咪唑基)苯硫醚(BIDPT)和邻苯二甲酸(H₂pht)为配体,合成了2个配位聚合物{[Zn(BIDPT)(pht)]₂·2H₂O·CH₃OH}_n(1)和{[Cd₅(BIDPT)₄(pht)₅]·H₂O}_n(2),分别用X-射线单晶衍射、元素分析和IR等手段对它们进行了表征。结果表明,配位聚合物1和2为2D层状结构,配位聚合物1属于正交晶系,Pbcn空间群;配位聚合物2属于三斜晶系,P2₁/c空间群。此外还考察了1和2的热稳定性和固体荧光性质。     

4-(3H)-喹唑酮Co(Ⅱ)、Ag(Ⅰ)配合物的合成、晶体结构、荧光和抗癌活性

以4(3H)-喹唑酮、Co(NO₃)₂·6H₂O、AgNO₃为原料,在相同物料比、溶剂和常温条件下,合成了配合物[Co(L)₂·(H₂O)₂·(NO₃)₂] (1)和[Ag(L)₂·(NO₃)] (2)(L=4-(3H)-喹唑酮).对其进行了X-射线单晶衍射表征和热重分析.X-射线单晶衍射分析表明,它们都属于三斜晶系,但1是六配位,2是三配位的.还测定了2的固体荧光和抗癌活性.配合物2的最大发射波长比配体红移了27 nm,其对NCI(人非小细胞肺癌细胞)有较好的抗癌作用.     

4-(3H)-喹唑酮Co(Ⅱ)、Ag(Ⅰ)配合物的合成、晶体结构、荧光和抗癌活性

以4(3H)-喹唑酮、Co(NO3)2·6H2O、Ag NO3为原料,在相同物料比、溶剂和常温条件下,合成了配合物[Co(L)2·(H2O)2·(NO3)2](1)和[Ag(L)2·(NO3)](2)(L=4-(3H)-喹唑酮)。对其进行了X-射线单晶衍射表征和热重分析。X-射线单晶衍射分析表明,它们都属于三斜晶系,但1是六配位,2是三配位的。还测定了2的固体荧光和抗癌活性。配合物2的最大发射波长比配体红移了27 nm,其对NCI(人非小细胞肺癌细胞)有较好的抗癌作用。     

Facile Synthesis of 2H-1,4-Benzothiazin-3(4H)-ketoximes and 2H-1,4-Benzoselenazin-3(4H)-ketoximes Promoted by SmI2

Abstract

2H-1,4-Benzothiazin-3(4H)-ketoximes and 2H-1,4-benzoselenazin-3(4H)-ketoximes were synthesized by the reductive cyclization of bis(o-nitrophenyl) disulfides or diselenides with aromatic or aliphatic β-nitroethylenes using SmI₂ in moderate to good yields under mild conditions.     

Ecofriendly and highly efficient microwave-induced synthesis of novel quinazolinone-undecyl hybrids with in vitro antitumor activity

Abstract

Novel N-alkyl-quinazolin-4-one derivatives 3–5 were obtained from reaction of 6-Iodo-2-undecylquinazolin-4(3H)-one (2) with different alkyl halides. Hydrazinolysis of compound 5 gave the acetohydrazide 6 which reacted with different carbon electrophiles to produce 2-undecyl-4(3H)-quinazolinone derivatives. The new products were obtained by either conventional method or by microwave assisting technique and the structure of all products was confirmed by elemental and spectral data. The ecofriendly microwave provides an efficiency over than conventional method in many aspects. All the synthesized products were tested in vitro against a panel of three human tumor cell lines, namely, hepatocellular carcinoma (liver) HepG2, colon cancer HCT-116, and mammary gland breast MCF-7. Almost all of the tested compounds showed satisfactory activity.