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1.
4,4'-联吡啶与二苄基二硫代氨基甲酸镉配合物[Cd(DBTC)2]2(1)反应得到加合物[Cd(DBTC)2(4,4'-bipy)](2)(DBTC=N,N-二苄基二硫代氨基甲酸),通过晶体结构分析及红外光谱等研究其结构与性质.结果表明:引入小分子配体会破坏[Cd(DBTC)2]2(1)的二聚结构,加入吡啶则得到单核的吡啶加合物[Cd(DBTC)2py](3),而引入4,4'-联吡啶后其结构变为新型的一维链状结构的配位聚合物2,这种结构在二硫代氨基甲酸金属配合物中少见报道.也比较了不同配体如吡啶及4,4'-联吡啶对Cd(Ⅱ)及Zn(Ⅱ)配合物结构的影响.  相似文献   

2.
0引言多原子桥联配体的多核配合物中,顺磁离子间磁偶合作用的研究对阐明磁性和结构的关系以及设计新型分子基磁性材料具有重要的理论意义。草酸根及草酰胺根桥联的多核配合物得到了较为广泛和深入的研究[1~5]。硫原子取代两个氧原子后,形成二硫代草酸根及二硫代草酰胺根,由于硫  相似文献   

3.
利用HF/6-31G*及半经验分子轨道AM1法,研究了硫代双烯酮及双三氟甲基硫代双烯酮二聚反应的反应机理,采用Berny梯度法优化得到反应的过渡态,并进行了振动分析确认,计算结果表明:(1)所有的二聚反应均是按照非同步的协同途径,经过扭曲的四元环过渡态进行的;(2)硫代双烯酮的二聚反应,三种可能的二聚方式中,生成对称四元杂环产物的二聚反应的活化焓最高;(3)双三氟甲基硫代双烯酮的二聚反应,生成对称四元杂环产物的二聚方式其活化焓比另外两种二聚方式的活化焓要低得多,这与实验中只观察到生成对称四元杂环产物的结果是一致的。  相似文献   

4.
使用2,2′-二硫代二苯甲酸和2,2′-联吡啶(2,2′-bipy)、硝酸铜在水热条件下发生的原位反应合成了一个铜配合物,即[Cu2(C14H8O4S)2(C10H8N2)2](1)(C14H8O4S=2,2′-二羧苯基硫醚,C10H8N2=2,2′-联吡啶);然后又利用2,2′-二硫代二苯甲酸和菲咯啉(phen)、氯化钙在水溶液中合成了一个钙配合物,即{[Ca(C14H8O4S2)(C12H8N2)2]·(H2O)2}n(2)(C14H8O4S=2,2′-二硫代二苯甲酸根,C12H8N2=菲咯啉),并对它们分别进行了元素分析、红外光谱、热稳定性、X射线粉末衍射和X射线单晶衍射的表征。结果表明:配合物1由2,2′-二羧苯基硫醚配体连接形成了一个双核的化合物,通过氢键和氮杂环之间的π…π作用形成三维超分子网络结构。配合物2由二硫代二苯甲酸配体桥联形成了一个一维链状结构,通过氢键和氮杂环之间的π…π作用也形成三维超分子网络结构。并且,对这2个配合物的热稳定性分别进行了研究。  相似文献   

5.
4,4'-联吡啶与二苄基二硫代氨基甲酸镉配合物[Cd(DBTC)2]2 (1)反应得到加合物[Cd(DBTC)2(4,4'-bipy)] (2) (DBTC=N,N-二苄基二硫代氨基甲酸), 通过晶体结构分析及红外光谱等研究其结构与性质. 结果表明: 引入小分子配体会破坏[Cd(DBTC)2]2 (1)的二聚结构, 加入吡啶则得到单核的吡啶加合物[Cd(DBTC)2py] (3), 而引入4,4'-联吡啶后其结构变为新型的一维链状结构的配位聚合物2, 这种结构在二硫代氨基甲酸金属配合物中少见报道. 也比较了不同配体如吡啶及4,4'-联吡啶对Cd(II)及Zn(II)配合物结构的影响.  相似文献   

6.
徐保莲  代坤  陈景文 《无机化学学报》2014,30(12):2733-2739
设计合成了4种含不同芳香取代基团的肼基二硫代甲酸甲酯配体(2-乙酰基吡啶肼基二硫代甲酸甲酯(L1-H)、2-甲酰基吡啶肼基二硫代甲酸甲酯(L2-H)、2-甲酰基噻吩肼基二硫代甲酸甲酯(L3-H)、2-甲酰基水杨醛肼基二硫代甲酸甲酯(L4-H))的镓配合物,对它们的抑菌活性进行了测试,并讨论了配体分子中不同芳香取代基对配合物抑菌活性的影响。在模拟生理条件下,L-H与Ga3+生成较稳定的单核配合物[Ga(L1)2]NO3(1)、[Ga(L2)2]NO3(2)、[Ga(L3)2]NO3(3)、[Ga(L4)2]NO3(4),各配合物对金黄色葡萄球菌和大肠杆菌表现出比Ga(NO3)3·9H2O强的抑制活性,抑制金黄色葡萄球菌的能力高于大肠杆菌,其中,1和2的活性比相应配体高,其余2个配合物与其配体之间无明显活性差异。L1-H和L2-H分子中吡啶基的较强吸电子效应可能是1和2具有较强抑菌活性的主要原因。4种配合物抑制黑曲霉生长的活性同样高于Ga(NO3)3·9H2O,其中3最强,并显著高于L3-H,其余配合物与相应配体间无活性差异。  相似文献   

7.
N,N-二甲酰基二硫代氨基甲酸根金属配合物的研究   总被引:3,自引:0,他引:3  
本文首次报道了一系列N,N-二甲酰基二硫代氨基甲酸根为配体的过渡金属配合物,对它们进行了化学分析、光谱表征和磁性质研究。研究结果表明,在配合物中,配体二硫代氨基甲酸根一般为较弱的双齿配位。  相似文献   

8.
孙海英 《化学研究》2000,11(2):28-30
合成和表征了新的含硫席夫碱—安息香缩肼基二硫代甲酸甲酯 (H2 L)及与Mn(Ⅱ ) ,Co(Ⅱ ) ,Ni(Ⅱ )Zn(Ⅱ )和Cd(Ⅱ )生成的配合物 [M(HL) 2 ]。结果表明这些配合物中安息香缩肼基二硫代甲酸甲酯存在为去质子化的烯硫醇式三齿配体 ,通过甲亚胺基氮原子、醇羟基氧原子和烯硫醇硫原子配位 ,金属离子处于六配位的八面体环境。  相似文献   

9.
潘庆才  彭正合 《化学通报》2000,63(12):40-44,56
各种均一配体的金属二硫纶[1~4]、金属二亚胺[5,6]以及二硫纶和二亚胺混合配体的金属配合物[7,8],因其具有特殊的氧化还原性和光、电、磁功能,近10多年来一直受到科学家们的高度重视.笔者的兴趣在于二氰基二硫纶(mnt2-)的过渡金属配合物,以及二氰基二硫纶和α,α′-二亚胺混合配体过渡金属配合物的合成、性质、结构和电子功能研究[9~12].这些配合物不仅本身具有优异的气敏、光敏、催化等功能性,而且也是合成金属四氮杂卟啉的前驱物[13~14]和自组装有序分子聚集体的功能元件之一[15].……  相似文献   

10.
用溶液法合成了4-(4′-吡啶)-1,3-二硫代环戊烯-2-酮(C8H5NOS2)与铜(Ⅱ)的配合物,并得到了单晶.通过红外光谱、元素分析和X射线单晶衍射分析对配合物的组成和结构进行了表征.X射线单晶衍射分析表明:配合物属三斜晶系,空间群P-1,是由2个CuSO4、4个配体C8H5NOS2分子、2个配位H2O和6个游离的H2O组成的双核配合物.配合物分子通过S…S短程作用形成了1个二维层状结构,并通过分子间的氢键作用进一步形成了更稳定的三维结构.  相似文献   

11.
A series of silver(I) supramolecular complexes, namely, {[Ag(L24)](NO3)}n ( 1 ), [Ag2(L24)(NO2)2]n ( 2 ), and {[Ag1.25(L24)(DMF)](PF6)1.25}n ( 3 ) were prepared by the reactions of 1‐(2‐pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazole (L24) and silver(I) salts with different anions (AgNO3, AgNO2, AgPF6). Single‐crystal X‐ray diffraction indicates that 1 – 3 display diverse supramolecular networks. The structure of dinuclear complex 1 is composed of a six‐membered Ag2N4 ring with the Ag ··· Ag distance of 4.4137(3) Å. In complex 2 , the adjacent AgI centers are interlinked by L24 ligands into a 1D chain, the adjacent of which are further extended by the bridged nitrites to construct a 2D coordination architecture. Complex 3 shows a 3D (3,4)‐connected framework, which is generated by the linkage of L24 ligands. All complexes were characterized by IR spectra, elemental analysis, and powder X‐ray diffraction. Notably, a structural comparison of the complexes demonstrates that their structures are predominated by the nature of anions. Additionally, 1 and 2 show efficient dichromate (Cr2O72–) capture in water system, which can be ascribed to the anion‐exchange.  相似文献   

12.
Poly[[μ4‐4,4′‐bipyridazine‐μ5‐sulfato‐disilver(I)] monohydrate], {[Ag2(SO4)(C8H6N4)]·H2O}n, (I), and poly[[aqua‐μ4‐pyridazino[4,5‐d]pyridazine‐μ3‐sulfato‐disilver(I)] monohydrate], {[Ag2(SO4)(C6H4N4)(H2O)]·H2O}n, (II), possess three‐ and two‐dimensional polymeric structures, respectively, supported by N‐tetradentate coordination of the organic ligands [Ag—N = 2.208 (3)–2.384 (3) Å] and O‐pentadentate coordination of the sulfate anions [Ag—O = 2.284 (3)–2.700 (2) Å]. Compound (I) is the first structurally examined complex of the new ligand 4,4′‐bipyridazine; it is based upon unprecedented centrosymmetric silver–pyridazine tetramers with tetrahedral AgN2O2 and trigonal–bipyramidal AgN2O3 coordination of two independent AgI ions. Compound (II) adopts a typical dimeric silver–pyridazine motif incorporating two kinds of square‐pyramidal AgN2O3 AgI ions. The structure exhibits short anion–π interactions involving noncoordinated sulfate O atoms [O...π = 3.041 (3) Å].  相似文献   

13.
Trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes [Ag3(μ‐dppm)3n‐SR)2](ClO4) [n = 2, R = C6H4Cl‐4 ( 1 ) and C{O}Ph ( 2 ); n = 3, R = tBu ( 3 )], pentanuclear silver(I) thiolate complex [Ag5(μ‐dppm)43‐SC6H4NO2‐4)4](PF6) ( 4 ), and hexanuclear silver(I) thiolate complexes [Ag6(μ‐dppm)43‐SR)4]Y2 [Y = ClO4, R =C6H4CH3‐4 ( 5 ) and C10H7 (2‐naphthyl) ( 7 ); Y = PF6, R = C6H4OCH3‐4( 6 )], were synthesized [dppm = bis(diphenylphosphanyl)methane] and their crystal structures as well as photophysical properties were studied. In the solid state at 77 K, trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes 1 and 2 exhibit luminescence at 470–523 nm, tentatively attributed to originate from the 3IL (intraligand) of thiolate or thiocarboxylate ligands, whereas hexanuclaer silver(I) thiolate complexes 5 and 7 produce dual emission, in which high‐energy emission is tentatively attributed to come from the 3IL of thiolate ligands and low‐energy emission is tentatively assigned to come from the admixture of metal ··· metal bond‐to‐ligand charge‐transfer (MMLCT) and metal‐centered (MC) excited states.  相似文献   

14.
The ditopic ligand 1, 2‐bis(benzimidazol‐1‐ylmethyl)benzene (L1) as well as its silver(I) complexes [Ag2L12(CF3CO2)2] ( 1 ) and [Ag2L12](CF3SO3)2 · (L1) · 2H2O · 0.5C2H5OH ( 2 ) were prepared and structures characterized by X‐ray crystallography. The AgI atoms in 1 are trigonally coordinated by two NBIm atoms from the arms of L1 and by one O atom of the anion CF3CO2, while those in 2 are only linearly ligated by NBIm. Different silver salts of CF3CO2 and CF3SO3 lead to different configurations of the dimeric unit [Ag2L12]2+: chair‐form in ( 1 ) but boat‐form in ( 2 ). The discrete molecules in both 1 and 2 are assembled into network structures through face‐to‐face π · · · π stacking and edge‐to‐face C—H · · · π interactions in the crystalline state, as well as N—H · · · O and C—H · · · O hydrogen bonds. Solution 1H NMR studies showed the formation of one sole species in solution or a rapid equilibrium was established on the NMR time scale at room temperature.  相似文献   

15.
The reaction of 4,4′‐bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl (btmb) with silver(I) salts of BF4, NO3 and N3 led to the formation of four new silver(I) coordination polymers {[Ag(btmb)]BF4}n ( 1 ), {[Ag2(btmb)3](NO3)2(H2O)5}n ( 2 ), [Ag2(btmb)(N3)2]n ( 3 ), and [Ag(btmb)(N3)]n ( 4 ). Their coordination number varies from 2 (in 1 ) to 3 (in 2 ), 4 (in 3 ), and 5 (in 4 ). Different from the single chain structure of 1 , complex 2 displays a 1D ladder‐like double chain framework, whereas complex 3 exhibits a 2D layered architecture. Complex 4 has the same anion as complex 3 but shows a different metal‐to‐ligand ratio and a 1D double‐zigzag chain structure. Both 3 and 4 have Ag ··· Ag argentophilic interactions. The ligand btmb adopts both cis or trans configuration in the studied complexes. A trans‐ or cis‐btmb ligand link silver ions with Ag ··· Ag distances of ≈?18 and 13 Å, respectively. BF4 and NO3 are non‐coordinating anions in 1 and 2 . N3 is the bridging anion in 3 (1,3‐bridging fashion) and 4 (1,1‐bridging fashion). These findings suggest that the coordination numbers around the AgI ion correlate to the coordination abilities of anions and the btmb to silver ratio. In addition, the influence of anions on thermal stability were also investigated. This work is a good example that nicely supports the less explored field of anion‐dependent structures of complexes with non‐pyridyl ligands.  相似文献   

16.
Two new silver(I) 3D coordination polymers, namely [Ag3(2‐stp)(dpa)]n ( 1 ) and {[Ag2(2‐stp)(H2O)]?Hdpa}n ( 2 ) (2‐NaH2stp=sodium 2,5‐dicarboxysulfonate, dpa=di(pyridine‐2‐yl)amine) were synthesized. The complexes were characterized by elemental analysis, FT‐IR spectra, thermogravimetric analyses (TGA), and single‐crystal X‐ray diffraction. In complex 1 , three neighboring Ag ions are bridged by N‐ and O‐atom, forming a 3D coordination network. The molecular structure of 2 is cation? anion species, forming 3D host? guest supramolecular network with the [Hdpa]+ cations encapsulated in the nanochannels. The photoluminescence properties of the complexes were also investigated in the solid state at room temperature.  相似文献   

17.
The title complex, [Ag2(C7H5O2)2(C18H18F2N2)]n, is a dinuclear silver(I) compound with one inversion centre between pairs of Ag atoms and another at the mid‐point of the central C—C bond in the butane‐1,4‐diamine moiety. Each of the smallest repeat units consists of two silver(I) cations, two benzoate anions and one N,N′‐bis(2‐fluorobenzyl­idene)­butane‐1,4‐di­amine Schiff base ligand. Each AgI ion is three‐coordinated in a trigonal configuration by two O atoms from two benzoate anions and one N atom from a Schiff base ligand. The di‐μ‐benzoato‐disilver(I) moieties are linked by the bridging Schiff base ligand, giving zigzag polymeric chains with an [–Ag⋯Ag—N—C—C—C—C—N–]n backbone running along the b axis.  相似文献   

18.
A general class of C3‐symmetric Ag9 clusters, [Ag9S(tBuC6H4S)6(dpph)3(CF3SO3)] ( 1 ), [Ag9(tBuC6H4S)6(dpph)3(CF3SO3)2] ? CF3SO3 ( 2 ), [Ag9(tBuC6H4S)6(dpph)3(NO3)2] ? NO3 ( 3 ), and [Ag9(tBuC6H4S)7(dpph)3(Mo2O7)0.5]2 ? 2 CF3COO ( 4 ) (dpph=1,6‐bis(diphenylphosphino)hexane), with a twisted trigonal‐prism geometry was isolated by the reaction of polymeric {(HNEt3)2[Ag10(tBuC6H4S)12]}n, 1,6‐bis(diphenylphosphino)hexane, and various silver salts under solvothermal conditions. The structures consist of discrete clusters constructed from a girdling Ag9 twisted trigonal prism with the top and bottom trigonal faces capped by diverse anions (i.e., S2? and CF3SO3? for compound 1 , 2×CF3SO3? for compound 2 , 2×NO3? for compound 3 , and tBuC6H4S? and Mo2O72? for compound 4 ). This trigonal prism is bisected by another shrunken Ag3 trigon at its waist position. Interestingly, two inversion‐related Ag9 trigonal‐prismatic clusters are dimerized by the Mo2O72? ion in compound 4 . The twist is amplified by the bulkier thiolate, which also introduces high steric‐hindrance for the capping ligand, that is, the longer dpph ligand. Four more silver–sulfur clusters (namely, compounds 5 – 8 ) with their nuclearity ranging from 6–10 were solely characterized by single‐crystal X‐ray diffraction to verify the above‐described synergetic effect of mixed ligands in the construction of Ag9 twisted trigonal prisms. Surprisingly, only cluster 1 emits yellow luminescence at λ=584 nm at room temperature, which may be attributed to a charge transfer from the S 3p orbital to the Ag 5s orbital, or mixed with metal‐centered (MC) d10→d9s1 transitions. Upon cooling from 300 to 80 K, the emission intensity was enhanced along with a hypsochromic shift. The good linear relationship between the maximum emission intensity and the temperature for compound 1 in the range of 180–300 K indicates that this is a promising molecular luminescent thermometer. Furthermore, cyclic voltammetric studies indicated that the diffusion‐ and surface‐controlled redox processes were determined for compounds 1 and 3 as well as compound 4 , respectively.  相似文献   

19.
The synthesis and characterization of the first supramolecular aggregates incorporating the organometallic cyclo‐P3 ligand complexes [CpRMo(CO)23‐P3)] (CpR=Cp (C5H5; 1a ), Cp* (C5(CH3)5; 1b )) as linking units is described. The reaction of the Cp derivative 1a with AgX (X=CF3SO3, Al{OC(CF3)3}4) yields the one‐dimensional (1D) coordination polymers [Ag{CpMo(CO)2(μ,η311‐P3)}2]n[Al{OC(CF3)3}4]n ( 2 ) and [Ag{CpMo(CO)2(μ,η311‐P3)}3]n[X]n (X=CF3SO3 ( 3a ), Al{OC(CF3)3}4 ( 3b )). The solid‐state structures of these polymers were revealed by X‐ray crystallography and shown to comprise polycationic chains well‐separated from the weakly coordinating anions. If AgCF3SO3 is used, polymer 3a is obtained regardless of reactant stoichiometry whereas in the case of Ag[Al{OC(CF3)3}4], reactant stoichiometry plays a decisive role in determining the structure and composition of the resulting product. Moreover, polymers 3a, b are the first examples of homoleptic silver complexes in which AgI centers are found octahedrally coordinated to six phosphorus atoms. The Cp* derivative 1b reacts with Ag[Al{OC(CF3)3}4] to yield the 1D polymer [Ag{Cp*Mo(CO)2(μ,η321‐P3)}2]n[Al{OC(CF3)3}4]n ( 4 ), the crystal structure of which differs from that of polymer 2 in the coordination mode of the cyclo‐P3 ligands: in 2 , the Ag+ cations are bridged by the cyclo‐P3 ligands in a η11 (edge bridging) fashion whereas in 4 , they are bridged exclusively in a η21 mode (face bridging). Thus, one third of the phosphorus atoms in 2 are not coordinated to silver while in 4 , all phosphorus atoms are engaged in coordination with silver. Comprehensive spectroscopic and analytical measurements revealed that the polymers 2 , 3a , b , and 4 depolymerize extensively upon dissolution and display dynamic behavior in solution, as evidenced in particular by variable temperature 31P NMR spectroscopy. Solid‐state 31P magic angle spinning (MAS) NMR measurements, performed on the polymers 2 , 3b , and 4 , demonstrated that the polymers 2 and 3b also display dynamic behavior in the solid state at room temperature. The X‐ray crystallographic characterisation of 1b is also reported.  相似文献   

20.
The hydrothermal reactions of sodium o‐hydroxybenzoate with AgNO3 yield a novel stable Ag(I) s?‐complex supramolecular polymer, [Ag2(o‐HOPhCO2)2]n. The structure of [Ag2(o‐HOPhCO2)2] was solved by single crystal X‐ray diffraction analysis. It is monoclinic with space group P2Jc and unit cell parameters a=0.7394(2) nm, b= 0.8822(2) nm, c=1.0662(2) nm, β= 107.66(3)°, Z=4. The silver(I) atom is two‐coordinated by two carboxylic oxygen atoms of two o‐hydroxybenzoate ligands, and meanwhile, forms supramolecular interaction with one carbon atom of phenyl‐ring in the third o‐hydroxybenzoate group. The a‐form Ag…C supramolecular bond bridges [Ag2(o‐HOPhCO2)2] units into an infinite 2D layered polymer [Ag2(o‐HOPhCO2)2]n. The coordination sphere of the silver atom is best described as a distorted T‐shaped geometry.  相似文献   

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