基于3,5-二(3-吡啶)-4-氨基-1,2,4-三唑配体的Co(Ⅱ)和Cu(Ⅱ)配合物的合成与晶体结构（英文）

利用3,5-二(3-吡啶)-4-氨基-1,2,4-三唑(L)配体与Co(Ⅱ)/Cu(Ⅱ)盐室温下反应得到了一维的配位聚合物{[CoL(H_2O)_4]SO_4·H_2O}n(1)和单核配合物[Cu(hfac)2L2](2,hfac=hexafluoroacetylacetonate)。通过红外、元素分析及X射线单晶衍射等检测手段对所合成的配合物进行了表征。结构研究表明,配合物1中,配体L呈顺式构型,采取双齿配位方式桥联Co(Ⅱ)离子形成一维正弦链状结构,一维链通过多种氢键相互作用连接进一步形成三维网状结构;溶剂水分子和硫酸根阴离子通过氢键连接在框架上。配合物2中,配体L则采取单齿配位方式,与Cu(Ⅱ)离子形成离散型的单核结构,通过多重氢键作用进而连接成三维网状结构。     

基于吡嗪-吡啶-酰腙配体的三个配合物的制备及其荧光和光催化性能

合成了3个配合物{[Zn_3(L)_2(SO_4)_2(H_2O)_4]·H_2O}n(1)、{[Cd_2(L)_2(SO_4)(H_2O)]·H_2O}n(2)和{[Cd(L)I]·CH_3OH}n(3)(HL=N′-nicotinoylpyrazine-2-carbohydrazonamide),并通过单晶X射线衍射、红外、元素分析和粉末X射线衍射等手段进行表征。配合物1中,采用μ3-η1η1η1配位模式的SO_4~(2-)把Zn(Ⅱ)连接成无机网状二维平面(bc面),有机配体HL交错的分布在网状平面的两侧,这些二维层在分子间氢键的作用下形成三维超分子结构。配合物2是由配体HL连接[(Cd2)2(μ2-SO4)2]和Cd1两种节点形成的二维结构,相邻的二维层在π…π堆积作用下形成三维超分子结构。配合物3是一维的Z字链结构,这些一维链在氢键的连接作用下形成二维的超分子网络结构。光催化降解亚甲基蓝实验结果表明,在双氧水存在时配合物1~3均表现出很好的降解效果。     

基于3，4-乙撑二氧基噻吩环配体的铜/锌配合物的合成、晶体结构及性质

利用3,4-乙撑二氧基噻吩-2,5-二羧酸(H_2L_1)为主配体,2,2′-联吡啶(L_2)、4,4′-联吡啶(L_3)为辅配体,分别与二水合氯化铜、氯化锌通过溶剂热反应得到配合物{[Cu_2(L_1)_2(L_2)(H_2O)_2(DMF)]·3H_2O}n (1)(DMF=N,N-二甲基甲酰胺)和配合物{[Zn(L_1)(L_3)(H_2O)2]·H_2O}n (2)。通过X射线单晶衍射法、红外光谱、元素分析、紫外光谱、荧光光谱、热重分析等测试手段对其结构进行了表征与性质研究。单晶结构分析表明:配合物1是由L_1~(2-)桥联Cu~(2+)形成的二维层状结构,并进一步通过氢键作用形成三维网络结构。配合物2是由L_1~(2-)连接Zn~(2+)形成一维链,并进一步桥联4,4′-联吡啶形成为一维带状结构,通过配位水分子与配体氧原子的氢键作用及带与带之间的π-π堆积形成三维结构。荧光分析和热重分析结果分别表明配合物1和2均有良好的荧光性能和热稳定性。配合物1和2的最大发射波长分别为364和365 nm。     

基于三吡啶烯烃配体的一维配位聚合物:合成、结构及光电性质

在室温下,用三吡啶烯烃配体dipyridin-2-yl-(4-(2-pyridin-4-yl-vinyl)-phenyl)-amine(ppvppa)与银盐溶液反应,分别得到3个具有类似的一维链结构的配位聚合物{[Ag(ppvppa)]BF4}n(1)、{[Ag(ppvppa)]PF6}n(2)和{[Ag(ppvppa)]NO3}n(3)。在溶剂热条件下,用ppvppa与Ni(Ⅱ)反应,得到另一个以辅助羧酸配体桥联的一维配位聚合物{[Ni(ppvppa)(2,3-NDC)(H2O)]·2H2O}n(4)。对配合物1～4分别进行了元素分析、红外、热重、粉末X射线衍射、单晶X射线衍射等结构表征。配合物1～3呈现出由ppvppa连接Ag(Ⅰ)形成的阳离子一维双股链结构。配合物4呈现出由2,3-NDC配体桥联2个相邻的[Ni2(ppvppa)2(H2O)2]单元形成的中性一维双股链结构。含有Ag(Ⅰ)的配合物1～3表现出良好的荧光性质,而含Ni(Ⅱ)的配合物4没有荧光响应。选取配合物1和4作为代表,研究了它们的光电流响应性质。配合物1和4均表现出灵敏的阳极光电流响应,且在多次循环后仍保持稳定且可重复,其光电流值分别为2和6μA,明显强于空白ITO电极的光电流响应。     

丝氨酸Cu(Ⅱ)配合物的合成、结构分析及稳定性研究

本文合成了一个丝氨酸配合物{[Cu(H2O)3(C3H6NO3)]2SO4}n,并对其进行了结构分析。其属单斜晶系,中心离子呈现六配位的八面体结构,有很明显的姜-泰勒效应。该配合物通过丝氨酸的桥连作用形成了一维链,相邻的一维链通过氢键相互作用形成三维超分子结构。本文也对配合物的红外光谱和热稳定性进行了研究。     

基于N-乙酰-L-酪氨酸构筑的两例纯手性钴(Ⅱ)配合物的合成、结构及性质（英文）

利用手性配体N-乙酰-L-酪氨酸(Hacty)与钴盐通过溶液法合成了2例纯手性配合物{[Co(acty)(bpp)_2(H_2O)_2](NO_3)·2H_2O}_n(1)和{[Co_2(acty)_2(bpe)_3(H_2O)_3](Cl O_4)_2·4H_2O}_n(2)(bpp=1,3-联(4-吡啶)丙烷,bpe=1,2-联(4-吡啶)乙烷),并对它们进行了元素分析(EA)、红外光谱(IR)、紫外光谱(UV)、热重(TG)、粉末X射线衍射(PXRD)及X射线单晶衍射测定。配合物1属于单斜晶系P21空间群,六配位的Co(Ⅱ)离子被bpp配体连接形成一维右手螺旋链结构。配合物2属于三斜晶系P1空间群,六配位的双核Co(Ⅱ)离子被bpe配体连接形成一维带状链结构。在氢键的作用下,它们均形成三维超分子结构,深入讨论了不同构型的含N辅助配体对配合物结构的影响。此外,测定了2例手性配合物的圆二色(CD)光谱。     

两个含三唑环有机配体的Hg（Ⅱ）配聚物的合成、晶体结构及其荧光性质

以碘化汞为原料,分别与3,5-二(4-吡啶基)-1,2,4-三唑(L1),4-氨基-3,5-二(4-吡啶基)-1,2,4-三唑(L2)在N,N-二甲基甲酰胺(DMF)溶液中反应,合成了2个一维链状Hg(Ⅱ)配聚物{[Hg2I4(4-bpt)2]·3DMF}n(1),{[Hg2I4(L2)]·DMF}n(2)。用红外光谱、元素分析、X-射线单晶衍射对配合物进行了表征。X-射线单晶衍射表明,配聚物1中汞离子位于扭曲的配位四面体中心,相邻汞离子通过分别与L1的2个端基N原子配位,桥连形成了一维zig-zag链结构,碘离子占据配位四面体的剩余两配位点,配聚物1的一维链平行于bc平面。配合物2中汞离子位于扭曲的配位四面体中心,分别与L2的一个吡啶N原子和3个碘离子配位,其中2个碘离子充当桥联配体将相邻汞离子连接,形成了一维-Hg-I-Hg-I-的zig-zag链,相邻的-Hg-I-Hg-I-链进一步通过作为双齿配体的L2连接,形成一独特的一维双链梯状聚合物,配聚物2一维链平行于a方向。室温固态荧光测试显示,配聚物1在383.7nm处具有强的荧光发射,而配聚物2在299.7 nm和376.5 nm处具有强的荧光发射。     

两个含三唑环有机配体的Hg(Ⅱ)配聚物的合成、晶体结构及其荧光性质（英文）

以碘化汞为原料,分别与3,5-二(4-吡啶基)-1,2,4-三唑(L1),4-氨基-3,5-二(4-吡啶基)-1,2,4-三唑(L2)在N,N-二甲基甲酰胺(DMF)溶液中反应,合成了2个一维链状Hg(Ⅱ)配聚物{[Hg2I4(4-bpt)2]·3DMF}n(1),{[Hg2I4(L2)]·DMF}n(2)。用红外光谱、元素分析、X-射线单晶衍射对配合物进行了表征。X-射线单晶衍射表明,配聚物1中汞离子位于扭曲的配位四面体中心,相邻汞离子通过分别与L1的2个端基N原子配位,桥连形成了一维zig-zag链结构,碘离子占据配位四面体的剩余两配位点,配聚物1的一维链平行于bc平面。配合物2中汞离子位于扭曲的配位四面体中心,分别与L2的一个吡啶N原子和3个碘离子配位,其中2个碘离子充当桥联配体将相邻汞离子连接,形成了一维-Hg-I-Hg-I-的zig-zag链,相邻的-Hg-I-Hg-I-链进一步通过作为双齿配体的L2连接,形成一独特的一维双链梯状聚合物,配聚物2一维链平行于a方向。室温固态荧光测试显示,配聚物1在383.7nm处具有强的荧光发射,而配聚物2在299.7 nm和376.5 nm处具有强的荧光发射。     

基于联苯四羧酸的Zn(Ⅱ)配合物的合成、结构和性质

利用联苯四羧酸(H4bptc)和双三唑乙烷(bte)合成了2个配位聚合物{[Zn2(bptc)(DMF)2(H2O)]·DMF·H2O}n(1)和{[Zn(bte)(bptc)0.5]·DMF·0.5H2O}n(2)。化合物1为三维Pt S-拓扑结构,在该配合物中每个双核次级构筑单元(SBU){Zn2(O2CR)4}与4个联苯四酸配体相连,从而将配合物构筑成了三维MOF结构。化合物2为二维梯形结构,并通过弱氢键O…H-C将二维层连接为三维结构。同时对配合物的热稳定性和荧光特征进行了讨论。     

4,4′-联吡啶桥联的三个铜有机膦酸配合物的合成、结构及磁性（英文）

在水热条件下,以N-氧化-2-吡啶膦酸(H2L)为主配体,4,4′-联吡啶(bpy)为桥联配体,合成了3个铜有机膦酸配合物:{[Cu(L)(bpy)0.5(H_2O)]·2H_2O}n(1),{[Cu(HL)2(bpy)]·4H_2O}n(2)和{[Cu2(L)2(bpy)]·3H_2O}n(3)。配合物1中,相邻的铜离子由2个膦酸根连成二聚体,二聚体之间通过bpy桥联成一维链。配合物2中,单核[Cu(HL)2]被bpy连接成一维链。配合物3中,四聚体[Cu2(L)2]2被bpy连接成"砖块状"结构的二维层。磁性研究表明,配合物1和3中铜离子之间存在反铁磁性耦合。     

Flexible and shape-selective guest binding at Cu(II) axial sites in 1-dimensional Cu(II)-1,2-bis(4-pyridyl)ethane coordination polymers

A series of guest-binding Cu(II) coordination polymers, {[Cu(bpetha)2(acetone)2].2PF6}n (bpetha = 1,2-bis(4-pyridyl)ethane) (1), {[Cu(bpetha)2(DMF)2].2PF6}n (2), {[Cu(bpetha)(2)(MeCN)(2)].2PF6.2MeCN}n (3), {[Cu(bpetha)2(H2O)2].2PF6.3THF.2H2O}n (4), {[Cu(bpetha)2(H2O)2].2PF6.3dioxane}n (5), and {[Cu(bpetha)2(H2O)2].2PF6.2-PrOH.2H2O}n (6), have been synthesized and crystallographically characterized. Their framework stabilities and guest-exchange properties have also been investigated. All compounds form a similar framework motif, a "double chain", in which the bpetha ligands bridge Cu(II) centers to form 1-D [Cu(bpetha)2]n double chains. A variety of Lewis base guest molecules, such as H2O, acetone, DMF, MeCN, THF, dioxane, and 2-PrOH, are incorporated into the assembly of the 1-D double chains. These chains flexibly change their forms of assembly in a guest-dependent manner. Interestingly, acetone, DMF, and MeCN guests with a carbonyl or cyanide group coordinate directly to the axial sites of the Cu(II) centers; in contrast, THF, dioxane, and 2-PrOH guests with an ether or alcohol group are incorporated into the frameworks not via coordination bonds but via weak interactions (hydrogen bonds and van der Waals forces). This selectivity is probably due to steric effects at coordinated oxygen or nitrogen atoms of the guests. Crystal-to-crystal transformations triggered by guests are observed, during which guests coordinated to the Cu(II) axial sites are readily removed and replaced by other guests.     

Self-assembly of unprecedented [8+12] Cu-metallamacrocycle-based 3D metal-organic frameworks

[8+12]-metallamacrocycle-based 3D frameworks {[Cu(4)(pbt)(2)(SO(4))(2)(DMF)(2)(CH(3)OH)]·7H(2)O·DMF}(n) (1) and [12]-macrocycle 3D {[Cu(2)(pbt)(SO(4))(DMSO)(CH(3)OH)(2)]·5H(2)O·CH(3)OH}(n) (2) have been obtained. Both complexes display antiferromagnetic couplings and high catalytic activity in the oxidative coupling reaction of 1-ethynylbenzene and oxazolidin-2-one.     

Construction of 0D to 3D cadmium complexes from different pyridyl diimide ligands

Four semirigid ditopic ligands, N,N'-bis(3-pyridylmethyl)-pyromellitic diimide (L(1)), N,N'-bis(4-pyridylmethyl)-pyromellitic diimide (L(2)), N,N'-bis(3-pyridylmethyl)-naphthalene diimide (L(3)), and N,N'-bis(4-pyridylmethyl)-naphthalene diimide (L(4)), reacted with Cd(NO(3))(2) to result in four cadmium(II) complexes, namely, {[Cd(2)(L(1))(2)(NO(3))(4)(CH(3)OH)(4)]·H(2)O} (1), [Cd(L(2))(NO(3))(2)(CH(3)OH)(2)·Cd(2)(L(2))(3)(NO(3))(4)]·{4(HCCl(3))·2H(2)O}(n) (2), {[Cd(L(3))(2)(NO(3))(2)]}(n) (3), and {[Cd(L(4))(2)(NO(3))(2)]·2(CHCl(3))}(n) (4). These complexes have been characterized by elemental analyses, powder X-ray diffraction, thermogravimetric (TG) analyses, IR spectroscopy, and single-crystal X-ray diffraction. Structural analyses show that four types of structures are formed: (1) a discrete M(2)L(2) ring with two Cd ions and two cis-L(1) ligands comprising a zero-dimensional molecular rectangle (0D), (2) an unusual zigzag linear chain and a one-dimensional ladder existing simultaneously in the crystal lattice (1D), (3) a two-dimensional network of the (4,4) net structure (2D), and (4) an unusual chiral three-dimensional framework with 5-fold interpenetrating diamond (dia) topology (3D). In these complexes, the ligands exhibit different coordination modes and construct various architectures by bridging Cd(NO(3))(2) inorganic building blocks. These results suggest that structural diversity of the complexes is tunable by ligand modifications, that is, varying the ligand spacer bulkiness or substituent position of terminal group. Furthermore, gas adsorption measurements indicate that 4 possesses moderate CO(2) uptake and some adsorption selectivity for CO(2) over N(2).     

一维聚合物{[Co(N3)2(dps)2]·0.5H2O}n的合成,结构和磁性质

A coordination polymer {[Co(N3)2(dps)2]·0.5H2O}n (1) (dps=dipyridin-4-ylsulfane) with one dimensional chains has been synthesized and the structure and magnetic properties were characterized. Complex 1 crystallizes belongs to monoclinic system and has space group P21/c. The CoⅡ ion is six-coordinated and located at a compressed octahedral environment due to the Jahn-Teller effect. The ligand of dps bridges between Co Ⅱ ions producing the infinite chains of Co ? ? ? Co along a direction and, interestingly, four pyridy1 groups of dps ligands form a propeller-shaped coordination geometry around CoⅡ ion with the same spiral within the chain. These 1D chains are further linked through the hydrogen bonds to generate a 3D supermolecular network. Magnetic studies indicated that complex 1 shows very weak antiferromagnetic coupling between CoⅡ ions in low temperature.     

A family of new glutarate compounds: synthesis, crystal structures of: Co(H2O)5L(1), Na2[CoL2] (2), Na2[L(H2L)4/2] (3), {[Co3(H2O)6L2](HL)2}.4H2O (4), {[Co3(H2O)6L2](HL)2}.10H2O (5), {[Co3(H2O)6L2]L2/2}.4H2O (6), and Na2{[Co3(H2O)2]L8/2].6H2O (7), and magnetic properties of 1 and 2 with H2L = HOOC-(CH2)3-COOH

Seven new glutaric acid complexes, Co(H 2O) 5L 1, Na 2[CoL 2] 2, Na 2[L(H 2L) 4/2] 3, {[Co 3(H 2O) 6L 2](HL) 2}.4H 2O 4, {[Co 3(H 2O) 6L 2](HL) 2}.10H 2O 5, {[Co 3(H 2O) 6L 2]L 2/2}.4H 2O 6, and Na 2{[Co 3(H 2O) 2]L 8/2].6H 2O 7 were obtained and characterized by single-crystal X-ray diffraction methods along with elemental analyses, IR spectroscopic and magnetic measurements (for 1 and 2). The [Co(H 2O) 5L] complex molecules in 1 are assembled into a three-dimensional supramolecular architecture based on intermolecular hydrogen bonds. Compound 2 consists of the Na (+) cations and the necklace-like glutarato doubly bridged [ C o L 4 / 2 ] 2 - infinity 1 anionic chains, and 3 is composed of the Na (+) cations and the anionic hydrogen bonded ladder-like [ L ( H 2 L ) 4 / 2 ] 2 - infinity 1 anionic chains. The trinuclear {[Co 3(H 2O) 6L 2](HL) 2} complex molecules with edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 4 and 5 are hydrogen bonded into two-dimensional (2D) networks. The edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 6 are bridged by glutarato ligands to generate one-dimensional (1D) chains, which are then assembled via interchain hydrogen bonds into 2D supramolecular networks. The corner-shared linear [Co 3O 16] trioctahedra in 7 are quaternate bridged by glutarato ligands to form 1D band-like anionic {[Co 3(H 2O) 2]L 8/2} (2+) chains, which are assembled via interchain hydrogen bonds into 2D layers, and between them are sandwiched the Na (+) cations. The magnetic behaviors of 1 and 2 obey the Curie-Weiss law with chi m = C/( T - Theta) with the Curie constant C = 3.012(8) cm (3) x mol (-1) x K and the Weiss constant Theta = -9.4(7) K for 1, as well as C = 2.40(1) cm (3) x mol (-1) x K and Theta = -2.10(5) K for 2, indicating weak antiferromagnetic interactions between the Co(II) ions.     

新型吡啶基羧酸席夫碱配体镍配合物的合成和晶体结构

通过新合成的吡啶基羧酸席夫碱配体（5-(吡啶基-3-亚甲基氨基)间苯二甲酸H2L）,和镍盐反应制备了一个新的镍配合物{[Ni(HL)₂(H₂O)₂]·2H₂O}_n(1),利用元素分析及X-射线单晶衍射对其进行了表征。结构分析结果表明标题化合物属于三斜晶系,P1 空间群,晶胞参数为a=0.764 79(11) nm,b=0.870 49(13) nm,c=1.081 13(16) nm,α=85.583(2)°,β=82.614(2)°,γ=81.565(2)°,V=0.704 82(18) nm³,Z=1,D_c=1.586 g·cm^-3,μ=0.763 mm^-1,F(000)=350。在配合物的结构中,Ni(Ⅱ)的配位构型为畸变的八面体。配合物中每个配体通过羧酸氧和吡啶氮原子和金属配位形成一维链状结构,并通过体系中丰富的氢键作用链接成为三维框架并加以稳定。     

一种新型Ni(Ⅱ)配位聚合物的合成、晶体结构和性质研究

溶剂热法合成了1个新配位聚合物{[Ni(C18H18N4O5)(DMF)]·(DMF}n.通过元素分析、红外光谱、热重以及X-射线单晶洐射对其进行了表征.该晶体为正交晶系,Pna21空间群.该化合物中,C18H18N4O5配体通过5个配位原子以及相邻的溶剂分子DMF上的1个配位原子与Ni(Ⅱ)原子配位,形成了1个扭曲的八面体配位构型.热重分析表明该化合物在140℃开始发生分解.     

由异烟酰胺基间苯二甲酸根构筑的混核钴铕配位聚合物的合成、晶体结构及荧光性质

由水热法合成了一个混核金属配位聚合物{[CoEu₂(INAIP)₄(H₂O)₆]·2.5H₂O}_n(1)(INAIP^2-=异烟酰胺基间苯二甲酸根),并对其进行了元素分析、IR及X-射线衍射法表征。晶体结构研究表明：配合物1属于三斜晶系,P1 空间群。配合物1是由配体异烟酰胺基间苯二甲酸连接而成的二维双层状结构,该二维层通过氢键拓展为三维超分子结构。配合物1的荧光测试研究表明它具有典型的稀土铕离子红色荧光。     

Two metal complex derivatives of pyridine thiazole ligand: synthesis,characterization and biological activity

Transition Metal Chemistry - In this work, two new metal(II) complexes with ligand based on pyridine thiazolone group, [Zn(L)2(TsO)2]2DMF (1), {[Cd(L)(NO3)2H2O)]DMF}n (2) (where...     

Combination of magnetic susceptibility and electron paramagnetic resonance to monitor the 1D to 2D solid state transformation in flexible metal-organic frameworks of Co(II) and Zn(II) with 1,4-bis(triazol-1-ylmethyl)benzene

Two families of coordination polymers, {[M(btix)(2)(OH(2))(2)]·2NO(3)·2H(2)O}(n) [M = Co (1), Zn (2), Co-Zn (3); btix = 1,4-bis(triazol-1-ylmethyl)benzene] and {[M(btix)(2)(NO(3))(2)]}(n) [M = Co (4), Zn (5), Co-Zn (6)], have been synthesized and characterized. The two conformations of the ligand, syn and anti, lead to one-dimensional (1D) cationic chains or two-dimensional (2D) neutral grids. Extrusion of the water molecules of the 1D compounds results in an irreversible transformation into the 2D compounds, which involves a change in conformation of the btix ligands and a rearrangement in the metal environment with cleavage and reformation of covalent bonds. This structural transformation has been followed by electron paramagnetic resonance (EPR) and magnetic susceptibility measurements to monitor the minor modifications that the metal centers suffer.