3,5-二烷基-1,2,4-三唑衍生物构筑的两个Cu4I4簇配合物的合成、结构和荧光性质

以3,5-二甲(丙)基-4-氨基-1,2,4-三唑为配体,与CuI在H₂O/MeCN混合溶剂热合成了2个构型不同的Cu₄I₄超分子化合物{[Cu₂(aadmtrz) I₂]·CH₃CN}_n(1)和[Cu₂(dptrz) I]_n(2)(aadmtrz=4-((1-氨乙基)-氨基)-3,5-二甲基-1,2,4-三唑,dptrz=3,5-二丙基-1,2,4-三唑),并进行了元素分析,红外,X射线粉末衍射及单晶衍射等表征。2个配合物中Cu₄I₄构型不同,配合物1中,Cu₄I₄簇连结成一个8环椅式-椅式结构,通过配体连接成(4,4)二维菱形格子结构;而配合物2中,Cu₄I₄簇呈畸变的立方烷结构,构成了含有19.5%孔隙率三维孔洞聚合物,其结构可简化为(3,4)-连接的拓朴结构。同时,在常温下研究了2个配合物的固体荧光性质。     

3,5-二烷基-1,2,4-三唑衍生物构筑的两个Cu4I4簇配合物的合成、结构和荧光性质

以3,5-二甲（丙）基-4-氨基-1,2,4-三唑为配体,与CuI在H₂O/MeCN混合溶剂热合成了2个构型不同的Cu₄I₄超分子化合物{[Cu₂（aadmtrz）I₂]·CH₃CN}_n （1）和[Cu₂（dptrz）I]_n （2）（aadmtrz=4-（（1-氨乙基）-氨基）-3,5-二甲基-1,2,4-三唑,dptrz=3,5-二丙基-1,2,4-三唑）,并进行了元素分析,红外,X射线粉末衍射及单晶衍射等表征。2个配合物中Cu₄I₄构型不同,配合物1中,Cu₄I₄簇连结成一个8环椅式-椅式结构,通过配体连接成（4,4）二维菱形格子结构;而配合物2中,Cu₄I₄簇呈畸变的立方烷结构,构成了含有19.5%孔隙率三维孔洞聚合物,其结构可简化为（3,4）-连接的拓朴结构。同时,在常温下研究了2个配合物的固体荧光性质。     

多酸导向的间苯二酚杯[4]芳烃[Co8]配位笼的组装及电化学性质

基于多金属氧酸盐(POM)的超分子配位笼的设计和组装引起了广泛的研究兴趣,但在合成过程中仍然存在挑战。本文中,我们报道了一例基于POM-杯芳烃的大型[Co₈]配位笼[Co₈(MTR4A)₆Cl₈](α-SiW₁₂O₄₀)₂·30DMF·74EtOH (cage-1),该配位笼由6个碗状间苯二酚杯[4]芳烃(MTR4A)分子、8个Co(Ⅱ)阳离子、2个α-SiW₁₂O₄₀^4-抗衡阴离子和8个Cl^-阴离子组装而成。值得注意的是,α-SiW₁₂O₄₀^4-阴离子通过氢键夹在层与层之间,形成一个三维超分子结构。此外,作为锂离子电池的负极材料,cage-1表现出良好的锂离子存储能力。cage-1也能够实现对亚硝酸盐(NO₂^-)的还原和抗坏血酸(AA)的氧化,是一种具有高活性的双功能催化剂。     

多酸导向的间苯二酚杯[4]芳烃[Co8]配位笼的组装及电化学性质

基于多金属氧酸盐（POM）的超分子配位笼的设计和组装引起了广泛的研究兴趣,但在合成过程中仍然存在挑战。本文中,我们报道了一例基于POM-杯芳烃的大型[Co₈]配位笼[Co₈（MTR4A）₆Cl₈]（α-SiW₁₂O₄₀）₂·30DMF·74EtOH （cage-1）,该配位笼由6个碗状间苯二酚杯[4]芳烃（MTR4A）分子、8个Co(Ⅱ)阳离子、2个α-SiW₁₂O₄₀^4-抗衡阴离子和8个Cl^-阴离子组装而成。值得注意的是,α-SiW₁₂O₄₀^4-阴离子通过氢键夹在层与层之间,形成一个三维超分子结构。此外,作为锂离子电池的负极材料,cage-1表现出良好的锂离子存储能力。cage-1也能够实现对亚硝酸盐（NO₂^-）的还原和抗坏血酸（AA）的氧化,是一种具有高活性的双功能催化剂。     

一维链式三唑锰晶体的结构及磁性能研究

用1H-1,2,4-三唑-3,5-二羧酸(H3 dctrz)为配体,1,2,4,5-苯四羧酸(H4 btec)为辅助生长剂,设计合成了一维链式配合物[Mn(Hdctrz) (H2O)3)]n,通过元素分析,红外光谱和粉末衍射进行了常规表征,同步辐射光源衍射结构分析给出该配合物结晶于单斜晶系空间群P21/c,其中Mn离子与N、O原子采取稍微扭曲的八面体构型,相邻的锰离子通过μ1,4-Hdctrz桥联形成一维“之”字型结构,氢键在构筑与稳定三维网状结构起重要作用.变温磁化率测定表明该配合物中两个金属锰之间表现为弱的反铁磁作用(J=-0.0599(2) cm-1).     

Synthesis and Structure of a Ladder-like Co-crystal Cu~ICl with 3,5-Dipropyl-4-amino-1,2,4-triazole

Redox reaction of a mixture of CuCl2·2H2O, H3PO3 and dpatrz(3,5-dipropyl-4-amino-1,2,4-triazole) at room temperature yields one new compound, [Cu(Ⅰ)(μ2-dpatrz)2Cu(Ⅰ)Cl2], with two independent cis- and trans-propyl side chain molecules. Compound 1 crystallizes in monoclinic, space group P21/c with a = 7.474(1), b = 17.807(1), c = 18.851(1) , β = 108.32(1)o, V = 2381.7(2) 3, Z = 4, C16H32Cl2Cu2N8, Mr = 534.48, Dc = 1.491 g·cm-3, μ = 2.03 mm-1, F(000) = 1104, GOOF = 1.050, the final R = 0.0445 and w R = 0.1162 for 3162 observed reflections(Ⅰ 2δ(Ⅰ)). Compound 1 shows discrete dimeric structures(A and B) containing inversion centers and the Cu(Ⅰ) ions are coordinated in triangle geometries. The isomers are connected by N–H···Cl hydrogen bonds, chains with graph-set C(7) and rings R22(14) and C–H···π interactions into stair-step chains(Tapes A and B) running parallel to the [01–1] direction. The N–H···Cl hydrogen bonds result in chain and cyclic structures with graph-sets C22(17) and R34(18) linking tapes A and B to form two-dimensional networks along the [031] direction. Packing of crystal 1 is stabilized by rings R34(18) and weak C–H···Cl hydrogen bonds parallel to the [01–2] direction. Bond valence sum(BVS) and UV-Vis absorption spectra support the existence of Cu(Ⅰ) ions. Compound 1 exhibits extensive green blue phosphorescence in the solid state at room temperature.     

Construction and Photoluminescence Properties of Zn(Ⅱ)/Cd(Ⅱ) Complexes with 4-Amino-3,5-propyl-1,2,4-triazole Ligand

Reaction of ZnCl2 and 4-amino-3,5-propyl-1,2,4-triazole(dpatrz) or CdCl2, NaN3 and dpatrz, in aqueous solution at room temperature yields two neutral clusters: a dinuclear complex [Zn2(dpatrz)2Cl4](I) and a linear trinuclear complex, [Cd3(dpatrz)4(N3)2Cl4](Ⅱ). Both complexes have been characterized by X-ray single-crystal diffraction, powder XRD, IR, elemental analysis, TG and fluorescence analysis. Complex I crystallizes in orthorhombic, space group Pbca with a = 11.865(2), b = 14.464(3), c = 15.985(3) , V = 2743.4(9) 3, Z = 4, C16H32N8Cl4Zn2, Mr = 609.4, Dc = 1.475 g·cm3, μ = 2.16 mm-1, F(000) = 1248, GOOF = 1.091, the final R = 0.0295 and wR = 0.0665 for 1999 observed reflections(I 2σ(I)). Complex Ⅱ crystallizes in monoclinic, space group P21/c with a = 11.408(2), b = 15.211(3), c = 18.152(6) , β = 123.75(2)o, V = 2619.1(1) 3, Z = 2, C32H64N22Cl4Cd3, Mr = 1236.05, Dc = 1.567 g·cm3, μ = 1.46 mm-1, F(000) = 1244, GOOF = 1.042, the final R = 0.0444 and wR = 0.0913 for 3466 observed reflections(I 2σ(I)). The analysis of X-ray revealed that both structures lie about the inversion centers: complex I adopts two μ1,2-triazole bridges linking two Zn(Ⅱ) ions and Ⅱ forms a linear trinuclear structure with four μ1,2-triazoles and two μ1,1-N3- bridging modes. There are different coordinated geometries for three Cd(Ⅱ) ions in Ⅱ: one is coordinated with an octahedral environment, and the other two are distorted tetragonal pyramids(τ = 0.34). The hydrogen bonds of C–H···Cl and N–H···Cl lead to the discretes into a 3D supramolecular network in both compounds. The thermal stabilities and photoluminescence behaviors of them were also studied.     

Syntheses,Structures, and Luminescence Properties of Two New Open-framework Zinc Phosphites Based on 1,2,4-Triazole Derivatives

With 1,2,4-triazole derivatives as structure directing agents, two new openframework zinc phosphites, [Zn(atrz)(HPO_3)]_n(1) and [Zn(dmatrz)(HPO_3)]_n(2)(atrz = 4-amino-1,2,4-triazole, dmatrz = 4-amino-3,5-dimethyl-1,2,4-triazole) have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder and single-crystal X-ray diffractions. Both compounds are isostructure and crystallize in the P21/c space group of monoclinic system. Compound 1: a = 9.629(1), b = 7.384(1), c = 10.274(1) ?, β = 110.729(3)°, V = 683.26(2) ?~3, Z = 4, Mr = 229.44, Dc = 2.230 g/cm~3, F(000) = 456, S = 1.10, μ = 3.79 mm~(–1), R = 0.0181 and w R = 0.0466 for 1121 observed reflections((40) 2s((40))). Compound 2: a = 10.786(2), b = 8.921(1), c = 9.749(1) ?, β = 107.3°, V = 895.6(3) ?~3, Z = 4, Mr = 257.49, Dc = 1.910 g/cm~3, F(000) = 520, S = 1.00, μ = 2.90 mm~(–1), R = 0.018 and wR = 0.051 for 1581 observed reflections((40) 2s((40))). Both compounds are built up into 4.8-net 2D open-frameworks of vertex-linked Zn O4 and HPO_3 units(3.57 × 4.53 ?~2 for 1 and 4.43 × 5.90 ?~2 for 2). The structures consist of left-, right-handed helical chains that are connected through oxygen atoms to form an undulated 2D sheet stack, which can be topologically regarded as 4.8~2 nets. Solid-state luminescence properties and thermo gravimetric analyses of these two compounds were investigated, respectively.     

基于1,2,4-三唑与水桥联的双核镉配合物的合成、晶体结构及荧光性质

利用缓慢蒸发溶剂法合成了双核镉配合物[Cd2(dpatrz)2Br4(H2O)](dpatrz=3,5-丙基-4-氨基-1,2,4-三唑).通过元素分析、红外光谱和粉末衍射进行了常规表征,同步辐射光源衍射结构分析给出该配合物结晶于四方晶系空间群P42/n.Cdl中心为五配位[CdN2OBr,],呈扭曲的三角双锥几何构型,中心对称的两个Cd原子通过两个μ1.2-dpatrz和一个H2O分子桥连形成双核结构,氢键作用加强了空间结构的稳定性并形成一维链结构.对配合物的热重分析与室温下固体荧光也分别进行了研究.     

一维爬梯式1,10-邻菲咯啉氯化亚锡配合物的合成及晶体结构

用氯化亚锡和1,10-邻菲咯啉(phen)在酸性条件下自组装合成了一维爬梯式[SnⅡ(t-Cl)2(phen)]n(1),元素分析,红外光谱进行了常规表征,同步辐射光源衍射结构分析表明配合物的晶体结构属于单斜晶系、C2/c空间群.中心Sn2+采取了扭曲的六配位八面体{ SnN2Cl4}∶4个Cl-与1,10-邻菲咯啉上的2个N原子共同形成了顺式八面体构型.分子单体通过μ2-Cl桥联形成一维链状结构,进一步通过氢键与1,10-邻菲咯啉之间强烈的π-π堆积作用形成三维网状空间结构.另外,价键理论(BVS)计算结果证明配合物中Sn显示+2价.