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。     

基于水杨醛类席夫碱构筑的Fe(Ⅲ)、Co(Ⅲ)、混价Mn(Ⅱ)/Mn(Ⅲ)配合物的合成、晶体结构及磁性

以3-甲氧基水杨醛与乙醇胺缩合得到席夫碱化合物hmmpH_2(hmmpH_2=2-[(2-羟乙基亚氨基)甲基]-6-甲氧基苯酚),以hmmpH_2为配体合成了配合物[Fe_2(hmmp)_2(hmmpH)_2]·1.5CH_3CN·0.5H_2O(1)和[Co_2Na(hmmp)_2(N_3)_2(CH_3O)(CH_3OH)_2](2)。以3,5-二溴水杨醛与乙醇胺缩合得到化合物hmdbrpH_2(hmdbrpH_2=2-[(2-羟乙基亚氨基)甲基]-4,6-二溴苯酚),以hmdbrpH_2为配体合成了一个混价三核配合物[Mn(Ⅱ)Mn(Ⅲ)_2(hmdbrp)_2(O_2CPh)_4(CH_3OH)_2]·2CH_3CN·2CH_3OH(3)(HO_2CPh为苯甲酸)。对配合物分别进行了元素分析、X射线单晶衍射分析,还对1和3进行了磁性研究。单晶结构分析表明配合物1中2个六配位的Fe(Ⅲ)离子通过2个醇羟基氧原子相连形成二聚体结构,配合物2中Co(Ⅲ)也为六配位,通过2个甲醇中氧原子相连形成双核结构,配合物3为一混价三核锰结构,3个Mn离子呈线性排列。磁性测试表明配合物1中Fe(Ⅲ)离子之间存在反铁磁相互作用,配合物3的三核锰单元内Mn(Ⅱ)、Mn(Ⅲ)离子之间存在反铁磁相互作用。     

席夫碱类混价七核锰金属配合物的合成、表征及磁性

以3-乙氧基水杨醛缩乙醇胺席夫碱(H2L)为配体合成了2个新的七核锰配合物[Na2MnⅡMnⅢ6O2(L)6(N3)4(CH3COO)2]·4DMF(1)和[Na2MnⅡMnⅢ6O2(L)6(SCN)4(CH3COO)2]·2DMF (2),并对它们进行红外分析、元素分析、热重分析和单晶结构分析。单晶衍射结果表明,配合物1和2均为混价七核锰配合物,包含1个Mn2+和6个Mn3+。此外还研究了配合物1和2的磁学性质,磁性研究表明配合物1和2都表现出反铁磁作用。     

双Salamo型四肟配体构筑的锌(Ⅱ)配合物:合成,晶体结构和荧光性质（英文）

通过二水乙酸锌(Ⅱ)和双Salamo型四肟配体6,6′-二乙氧基-双(2,2′-(乙二氧双(氮次甲基)))四酚(H4L)的配位反应,合成了2种锌(Ⅱ)配合物即:[Zn_3(L)(OAc)2(H_2O)](1)和[Zn3(L)(OAc)2(H2O)]·[Zn3(L)(OAc)2(CH_3OH)(H_2O)]·3CH_3OH·H_2O(2)。该类配合物含有2个Salamo型L4-配体和3个锌(Ⅱ)离子,其中2个锌(Ⅱ)原子位于Salamo型螯合单元的N2O2空腔内。[Zn(L)]螯合物中桥联的酚氧原子进一步和中心的锌(Ⅱ)原子配位。这类结构能通过2个桥联的乙酸根配体稳定,从而使配合物1和2达到电荷平衡。配合物有2种不同的几何构型即扭曲的三角双锥和四方锥(配合物1)或三角双锥和八面体(配合物2)。另外,配合物1和2在激发波长为340和337 nm时能发出强的绿光,其最大发射波长分别为531和536 nm。     

含吡嗪的缩氨基脲配体Ni(Ⅱ)/Cd(Ⅱ)配合物的晶体结构及与DNA的相互作用（英文）

合成配合物[NiL_2]·CH_3OH·0.5H_2O(1)和[Cd(HL)Cl_2](2)(HL=3-甲基2-乙酰吡嗪缩4-苯基氨基脲)并通过单晶衍射、元素分析及红外光谱表征其结构。单晶衍射结果表明,配合物1中,Ni(Ⅱ)离子与2个拥有N_2O电子供体的阴离子配体L-配位,配位构型为扭曲的八面体。而配合物2中,Cd(Ⅱ)离子与1个中性三齿配体HL和2个氯离子配位,拥有扭曲的四方锥配位构型。荧光光谱结果表明,配合物与DNA的相互作用强于配体。     

2,2'-联吡啶-3,3'-二羧酸锰(Ⅱ)配合物的合成、晶体结构及性能研究

以2,2’-联吡啶-3,3’-二羧酸(H2L)和1,10-邻菲啰啉(Phen)为配体合成了一个新的锰(Ⅱ)配合物[Mn(H2O)(L)(Phen)2]· (H2O)3.该配合物晶体属单斜晶系,空间群P21/c.在配合物中,中心锰(Ⅱ)离子的配位数是6,处于变形的八面体配位环境中.还测定了标题配合物的磁性,荧光和电化学性能,结果表明:在低温下,配合物有反铁磁性;当激发波长为656 nm时,配合物在682 nm附近有一个宽的荧光发射峰;在循环伏安过程中配合物的电子转移是准可逆的,对应的电极反应是Mn(Ⅲ)/Mn(Ⅱ).     

水杨醛半卡巴腙锰配合物

以水杨醛半卡巴腙(H_2L)为配体合成了3种新型锰配合物:Mn(HL)_2·O.5H_2O、Mn(HL)L·1.5MeOH和Mn_3L_2(O_2CM_e)_4·3H_2O,并用元素分析、摩尔电导率、磁化率、红外光谱、紫外可见和ESR谱等对其组成和结构进行了研究和讨论。     

2-乙酰吡嗪缩肼基甲酸甲酯的镍和镉配合物的晶体结构及荧光性质（英文）

合成并通过X射线单晶衍射、元素分析及红外光谱表征了配合物[Ni(L)_2](1)和[Cd(HL)(CH_3OH)(NO_3)_2](2)的结构(HL为2-乙酰吡嗪缩肼基甲酸甲酯)。单晶衍射结果表明,配合物1中,Ni(Ⅱ)离子与来自2个阴离子配体L-的N_2O电子供体配位,形成扭曲的八面体配位构型。在配合物2中,Cd(Ⅱ)离子拥有双帽三棱柱配位构型,与1个中性配体HL,2个双齿配位硝酸根和1分子甲醇配位。此外还研究了配合物1和2的荧光及热性质。     

水、氯配位的Shiff碱单核及双核锰化合物的合成与结构表征

在水杨醛与二元胺形成的Schiff碱与Mn盐的反应体系中分离出两个单核Mn化合 物,(salen)Mn(H_2O)Cl(1)和[(salpr)Mn(H_2O)_2]Cl(2),并测定了结构。应用对 苯二甲酸在碱性条件下拉接两个单核Mn的Schiff碱配位单元,生成(salen)_2Mn_2 [μ-p-C_6H_4(COO)_2](H_2O)(CH_3OH)(3)并进行了结构表征。讨论了这些化合物 的红外及~1HNMR谱,揭示了Mn中心对配体信号的影响。     

基于希夫碱配体的线型三核过渡金属配合物的合成、晶体结构及磁学性质研究

以邻羟基苯乙酮和1,3-丙二胺为原料,合成了平面四齿螯合型希夫碱有机配体。利用此希夫碱配体分别与镍、铜、锌的水合醋酸盐在甲醇和乙腈的混合溶剂中反应,得到了三个希夫碱金属配合物Ni_3(L)_2(CH_3COO)_2]·2CH_3CN·4H_2O(1),[Cu_3(L)_2(CH_3COO)_2]·CH_3CN·2H_2O(2)and[Zn_3(L)_2(CH_3COO)_2]·2CH_3CN(3)。配合物1-3用元素分析、红外光谱和X-射线单晶衍射进行了表征。单晶结构分析表明,配合物1结晶于单斜晶系,而配合物2和3是同构的,属于三斜晶系。这三个配合物具有类似的线型三核结构,含有两种晶体学独立的金属离子,其配位环境分别为六配位变形八面体和五配位四方锥的几何构型。配合物1和2的变温磁化率测量表明,金属离子之间存在反铁磁相互作用。     

Silver(I)-organic networks constructed with flexible silver-ethynide supramolecular synthon o-, m-, p-Cl–C6H5OCH2CC⊃Agn (n = 4, 5)

A series of five silver coordination polymers [(AgL1)·(AgCF₃COO)₅·(H₂O)₃] (1), [(AgL1)₂·(AgCF₃COO)₁₁·(H₂O)₆] (2), [(AgL2)·(AgCF₃COO)₃·(H₂O)] (3), [(AgL3)·(AgCF₃COO)₄·(CH₃CN)₂] (4), and [(AgL3)·(AgCF₃COO)₇·(CH₃CN)₂·(H₂O)₂] (5) have been constructed from three flexible anionic ligands HL1, HL2, and HL3 (HL1 = 1-chloro-2-(prop-2-ynyloxy)benzene, HL2 = 1-chloro-3-(prop-2-ynyloxy)benzene, HL3 = 1-chloro-4-(prop-2-ynyloxy)benzene). In these compounds, the invariable appearance of the μ₄- and μ₅-ligation modes of the ethynide moiety affirms the general utility of the flexible silver-ethynide supramolecular synthon o-, m-, p-Cl?C₆H₅OCH₂CC?Ag_n (n = 4, 5) in coordination network assembly. Among them, Ag?Cl interaction plays a vital role in assembling the supramolecular structures in complexes 1?3.     

The physicochemical and biological properties of zinc(II) complexes

Spectroscopic (IR), thermoanalytical (TG/DTG, DTA) and biological methods were applied to investigate physicochemical and biological properties of seven zinc(II) complex compounds of the following formula Zn(HCOO)₂·2H₂O (I), Zn(HCOO)₂·tph (II), Zn(CH₃COO)₂·2H₂O (III), Zn(CH₃COO)₂·tph (IV), Zn(CH₃COO)₂·2phen (V), Zn(CH₃CH₂COO)₂·2H₂O (VI), Zn(CH₃CH₂CH₂COO)₂·2H₂O (VII), where tph=theophylline, phen=phenazone. The formation of various intermediates during thermal decomposition suggests the dependence on the length of aliphatic carboxylic chain and type of N-donor ligand (tph, phen). The final product of the thermal decomposition was ZnO. The antimicrobial activity of these complexes were tested against G⁺ and G^– bacteria. Strong inhibitive effect was observed towards E. coli, salmonellae and Staph. aureus.     

Complexation of 2,3-dihydroxyquinaline with some bivalent <Emphasis Type="Italic">d</Emphasis> metals. Crystal and molecular structures of 2,3-dihydroxyquinoline

The reactions of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Cd with 2,3-dihydroxyquinoline (H₂L) were used to synthesize and identify the complexes M(HL)₂ · 2H₂O (M = Mn, Ni, Cu), Fe(HL)OH · 2H₂O, Co(HL)OH · H₂O, Cd(H₂L)Cl₂, where H₂L participates in the coordination in the monoanionic or neutral forms with the formation of the chelate cycles. Single crystal was isolated and the crystal structure of H₂L was determined. The spectral characteristics of a neutral and anionic form of the ligand were measured, and its complexation with MCl₂ was studied in the ethanol solutions. The acidity constant of H₂L and the formation constants of the complexes in solutions were calculated.     

四个对苯酚四唑硫酮金属(II)配合物的合成和晶体结构

四唑酸(–CN4H)与羧酸(–COOH)具有相似的酸性。对苯酚四唑硫酮(H2L)可以作为单齿(–S或–N)或双齿(–N, N或–N, S)配体与金属离子配位形成配位化合物。合成了4个以H2L为配体的金属(II)配合物：Co(HL)2(Py)2(H2O)2 (1), [Mn(HL)2(H2O)4]·2H2O (2), Mn(HL)2(Phen)2 (3), and [Zn(HL)2(Phen)2]·0.5H2O·1.5CH3OH (4),并用X−射线单晶衍射法测定了晶体结构。晶体结构分析表明,在这些配合物中所有的中心金属原子均呈现六配位的八面体构型。在配合物1和2中,HL–配体以氧原子与中心金属原子配位,而在配合物3和4中HL–配体则以硫原子与中心金属原子配位。     

Syntheses,structures, and properties of supramolecular complexes with bipyridine and amino-Schiff-base derived from salicylaldehyde with glycine

The reactions of stoichiometric amounts of Cu(CH₃COO)₂ · 2H₂O or Ni(CH₃COO)₂ · 2H₂O with KHL (potassium salt of salicylideneglycine) and 4,4′-bipy or 2,2′-bipy ethanol afforded [Cu₂(L)₂(μ-4,4′-bipy)(4,4′-bipy)₂] · 2H₂O (1) (L = salicylideneglycine) and Ni(OAc)₂(2,2′-bipy) (H₂O)₂ (2), respectively. The structure of 1 contains two Cu(II)'s, bridged by 4,4′-bipy; each copper is square pyramidal. Complex 2 contains a Ni(II) in highly distorted octahedral geometry. The two complexes were constructed into 3-D interwoven networks by typical H-bonding (i.e., O?H ··· O and N?H ··· O) and some other intra- or intermolecular weak interactions (i.e., C?H ··· O).     

Thermal stability of new zinc acetate-based complex compounds

New zinc acetate based complex compounds (of general formula Zn(CH₃COO)₂·1?2L·nH₂O) containing one or two molecules of urea, thiourea, coffeine and phenazone were prepared namely: Zn(CH₃COO)₂·2.5H₂O, Zn(CH₃COO)₂·2u·0.5H₂O, Zn(CH₃COO)₂·tu·0.5H₂O, Zn(CH₃COO)₂·2tu, Zn(CH₃COO)₂·cof·2.5H₂O, Zn(CH₃COO)₂·2cof·3.5H₂O, Zn(CH₃COO)₂·2phen·1.5H₂O. The compounds were characterized by IR spectroscopy, chemical analysis and thermal analysis. Thermal analysis showed that no changes in crystallographic modifications of the compounds take place during (heating in nitrogen before) the thermal decompositions. The temperature interval of the stability of the prepared compounds were determined. It was found that the thermal decomposition of hydrated compounds starts by the release of water molecules. During the thermal decomposition of anhydrous compounds in nitrogen the release of organic ligands take place followed by the decomposition of the acetate anion. Zinc oxide and metallic zinc were found as final products of the thermal decomposition of the zinc acetate based complex compounds studied. Carbon dioxide and acetone were detected in the gaseous products of the decomposition of the compounds if ZnO is formed. Carbon monoxide and acetaldehyde were detected in the gaseous products of the decomposition, if metallic Zn is formed. It is supposed that ZnO and Zn resulting from Zn acetate complex compounds here studied, possess different degree of structural disorder. Annealing takes place by further heating above 600°C.     

Study on the equilibrium in the M(CH3COO)2 ? CH3OH ? H2O system (M  Mg2+, Ca2+, Ba2+) at 25°C

The complex formation and dehydration processes in the system M(CH₃COO)₂? CH₃OH? H₂O have been studied by the methods of the physico-chemical analysis at 25°C; (M = Mg²⁺, Ca²⁺ and Ba²⁺). In the Mg(CH₃COO)₂? CH₃OH? H₂O system. methanol was found to behave as a solvent in which complex formation reactions take place, including also methanolation of Mg²⁺. The fields of equilibrium existence of two new compounds have been found: Mg(CH₃COO)₂ · 3H₂O · CH₃OH and Mg(CH₃COO)₂ · 1,5 CH₃OH. In the systems M(CH₃COO)₂? CH₃OH? H₂O (M = Ca²⁺, Ba²⁺), methanol was found to react as a dehydrating reagent.     

Coordination compounds of cobalt, nickel, copper and zinc with thiosemicarbazone and 3-phenylpropenal semicarbazone

Hydrates of 3-phenylpropenal thiosemicarbazone (HL·H₂O) and semicarbazone (HL′·H₂O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX₂·2HL·nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO₃; HL = C₆H₅CH=CH-CH=N-NHC(O)NH₂; n = 0–3; Solv = H₂O, CH₃OH], CuX₂·HL·nH₂O [M = Ni, Cu; n = 0, 1], ML₂·nH₂O and ML′·nH₂O [M = Co, Ni, Zn; HL′ = C₆H₅CH=CH-CH=N-NHC(O)NH₂; n = 0–3]. In the presence of amines (A = C₅H₅N, 2-CH₃C₅H₄N, 3-CH₃C₅H₄N, and 4-CH₃C₅H₄N) these reactions yield the complexes Cu(A)LCl·CH₃OH and M(A)LX·nH₂O [M = Cu, Ni; X = Cl, NO₃; n = 0–2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL′) are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70–90°C), deaquation (150–170°C), and full thermal decomposition (500–580°C).     

Tb(III) complexes with 1-phenyl-3-methyl-4-stearoyl-pyrazol-5-one as a material for luminescence Langmuir–Blodgett films

Abstract

Synthesis and properties of new luminescent amphiphilic Tb(III) complexes [TbL₃·2H₂O]·3H₂O, TbL₃·bipy, [H₃O][TbL₄]·6H₂O and [H₃O][TbL′₃L]·H₂O, where HL is 1-phenyl-3-methyl-4-stearoylpyrazolone-5 and HL′ is 1-phenyl-3-methyl-4-formylpyrazolone-5, are reported. The complexes have been characterized by elemental and thermal analysis, FTIR and luminescence spectroscopy methods. Formation and properties of Langmuir–Blodgett films of the complexes are described.