A Novel Three-dimensional Triazole-based Zinc(Ⅱ) Coordination Polymer Controlled by the Spacers of Dicarboxylate Ligand with(4~2,6~2,8~2)(4,6~2,8~3) Topology

A novel mixed-ligand coordination polymer [Zn(BTA)(ip)0.5]n(1, HBTA = benzotriazole, H2 ip = isophthalic acid) has been synthesized under hydrothermal conditions, which was further characterized by X-ray diffraction, IR spectrum, elemental analysis and TG-DTA experiments. Complex 1 crystallizes in monoclinic system, space group Pnma with a = 8.9731(5), b = 22.0477(12), c = 10.0217(5) ?, V = 1982.66(18) ?3, Z = 8, C10 H6 ZnN3 O2, Mr = 265.55, Dc = 1.779 g/cm3, μ = 2.462 mm-1, F(000) = 1064, the final R = 0.0225 and wR = 0.0652 with I 2?(I). This complex is a 3 D framework with the(42,62,82)(4,62,83) topology. Furthermore, the thermal stability of complex 1 is observed to be dependent on the polymeric structure nature. Strong solid-state luminescence emissions suggest that complex 1 is a good candidate for light emission materials.     

一系列由柔性N,N''-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)4](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}_n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)2·9H₂O}_n (5),其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构,配合物5为二维层状结构,其中金属离子由质子化的bpma配体桥连。值得注意的是,采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构,配合物3和4为螺旋链结构,配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

基于1-(1′，3′-苯并噁唑-2′-甲基)苯并咪唑的钴(Ⅱ)配合物：晶体结构、弱相互作用和荧光发射光谱

配体1-(1′,3′-苯并恶唑-2′-甲基)苯并咪唑(L)是通过苯并咪唑与2-(氯甲基)-1,3-苯并恶唑烷基化制备而来。配体L与CoCl2.2H2O反应得到了配合物[CoCl2L2](1)。配合物1通过π-π堆积作用和C-H…Cl氢键形成了三维超分子框架结构。测定了L和1的荧光发射光谱。     

4-(1,2,4-三唑-1-基)苯酚铜(Ⅱ)/镍(Ⅱ)配合物的晶体结构及荧光性质（英文）

合成并通过单晶和粉末X射线衍射、元素分析、红外光谱、热失重以及荧光光谱技术表征了含有4-(1,2,4-三唑-1-基)苯酚(hptrz)配体的2个过渡金属配合物{[Ni(H_2O)_2(hptrz)_2(tp)]·2DMF}_n(1)和[Cu(hptrz)_2(SCN)_2]·2H_2O (2)(H_2tp为对苯二甲酸)。配合物1中八面体的Ni(Ⅱ)离子由tp~(2-)阴离子拓展形成线性的一维链状结构;而配合物2则呈现中心对称的单核结构。配合物中,中性的hptrz配体呈现端基配位模式,并通过形成O-H…O氢键相互作用将低维结构拓展为高维超分子网络。此外,配体内的电荷转移使这2个配合物均在紫外区发射出强的荧光发射峰。     

一个对2,4,6-三硝基苯酚和Fe3+离子具有双重荧光传感行为的层状镉(Ⅱ)-有机配位聚合物

通过水热法合成了一个由三连接的2,3-喹啉二甲酸桥联扭曲的Cd²⁺八面体形成的二维层状配位聚合物[Cd（QDA）]_n（1）。该配合物发射出较强的蓝色荧光并具有很高的热稳定性和化学稳定性。更为重要的是,该配合物在乙醇分散体系中可快速识别痕量的2,4,6-三硝基苯酚和Fe³⁺离子,其对2,4,6-三硝基苯酚的淬灭常数（K_sv）和检测限（LOD）分别为6.61×10⁴ L·mol^-1和0.83 μmol·L^-1,对Fe³⁺离子的淬灭常数和检测限分别为1.74×10⁴ L·mol^-1和2.70 μmol·L^-1。     

基于1-丁基苯并咪唑和对苯二甲酸混合配体的锌(Ⅱ)和铜(Ⅱ)一维配位聚合物:晶体结构和弱相互作用(英文)

用1-丁基苯并咪唑和对苯二甲酸与Zn(NO3)2.6H2O或Cu(NO3)2.3H2O反应合成了两个锌(Ⅱ)和钴(Ⅱ)的一维配位聚合物[Zn(L)2(TP)]n(1)和[Cu(L)2(TP)]n(2)(L=1-丁基苯并咪唑,TP=对苯二甲酸根)。配位聚合物1和2通过C-H…O或O-H…O氢键形成了二维超分子层。测定了L,1和2的荧光发射光谱。     

Syntheses and Crystal Structures of Two Cadmium(Ⅱ) Compounds Linked by N,N-Bis(3-pyridylmethyl)amine

Two cadmium(Ⅱ) compounds linked by a flexible dipyridyl ligand {[Cd2(Hbpma) Cl5(H2O)]·2H2O}n 1 and [Cd(Hbpma)Cl(H2O)2]2·2SO4·3H2O 2 (bpma = N,N-bis(3-pyridylmethyl)amine) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P with a = 9.5612(6), b = 11.3401(7), c = 11.5069(12), α = 112.8540(10), β = 106.5330(10), γ = 101.6680(10)°, V = 1030.77(14)3, C12H20Cd2Cl5N3O3, Mr = 656.36, Z = 2, Dc = 2.115 g/cm3, μ(MoKα) = 2.727 mm-1, F(000) = 636, S = 1.059, the final R = 0.0319 and wR = 0.0822 for 3443 observed reflections (I > 2σ(I)). For complex 2, it belongs to triclinic, space group P with a = 10.9487(4), b = 11.4197(4), c = 15.4288(5), α = 94.7470(10), β = 104.1000(10), γ = 104.42°, V = 1790.76(11)3, C24H42Cd2Cl2N6O15S2, Mr = 1014.46, Z = 2, Dc = 1.881 g/cm3, μ(MoKα) = 1.529 mm-1, F(000) = 1020, S = 1.050, the final R = 0.0178 and wR = 0.0451 for 6026 observed reflections (I > 2σ(I)). Complex 1 is found to have tetranuclear Cd(Ⅱ) clusters which are bridged by the protonated bpma ligands leading to one-dimensional coordination polymers, whereas complex 2 consists of binuclear Cd(Ⅱ) structures linked by the protonated bpma ligands. Both complexes are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions.     

一系列由柔性N,N'-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)₄](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)₂·9H₂O}_n (5), 其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构, 配合物5为二维层状结构, 其中金属离子由质子化的bpma配体桥连。值得注意的是, 采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构, 配合物3和4为螺旋链结构, 配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

Two Preparation Methods-dominated Cd~(Ⅱ)-Based Coordination Polymers with Mixed Adenine Nucleobase and 5-Nitroisophathalate Ligands: Synthesis,Structure and Fluorescence

Two new CdⅡ-based coordination polymers(CPs) with mixed adenine(Hade) nucleobase and 5-nitroisophathalate(nip) ligands, {[Cd(Hade)_(0.5)(H_2O)_2(nip)]·H_2O}n 1 and {[Cd(Hade)(H_2O)_(1.25)(CH_3OH)0.75(nip)]·0.75 CH_3OH·0.5H_2 O}_n 2, were successfully obtained by varying the preparation methods and structurally characterized. Crystal data for 1: monoclinic, C2/c space group with a = 10.5546(6), b = 17.3496(6), c = 16.1198(9) ?, β = 104.2800(10)o, V = 2860.6(2) ?3, Dc = 2.058 g/cm~3, Mr = 443.13, Z = 8, F(000) = 1752, μ = 1.585 mm~(–1), the final R = 0.0394 and wR = 0.1109 for 2285 observed reflections with I 2σ(I). For 2: triclinic, P1 space group with a = 10.2032(7), b = 10.5098(8), c = 11.0223(8) ?, a = 65.7050(10)o, β = 74.5750(10)o, g = 61.5280(10)o, V = 943.38(12) ?~3, Dc = 1.888 g/cm3, Mr = 536.24, Z = 2, F(000) = 537, μ = 1.225 mm~(–1), the final R = 0.0225 and wR = 0.0702 for 3143 observed reflections with I 2σ(I). 1 presents a crisscrossed layer with mutually orthogonal {Cd(nip)} chains aggregated by neutral m-N(7),N(9)-Hade connector. By contrast, 2 displays a linear chain with CdⅡ ions extended by bis-bidentate chelating-nip2–connectors, which are further assembled into a broad ribbon by N-H···N hydrogen-bonding interactions. Additionally, the two solid-state samples with comparable thermal stability exhibit favorable luminescent emissions at room temperature, suggesting their potential applications as fluorescence materials.     

A New Pillared-layer Framework with Co^Ⅱ 4-Triazole Magnetic Layer Exhibiting Strong Spin-frustration

One new coordination polymer, [Co4(H2 O)4(μ3-OH)2(atz)2(L)]n(1), was solvothermally prepared by the reaction of 3-amino-1,2,4-triazole(Hatz), 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid(H4 L) and Co^Ⅱ salt. It crystallizes in monoclinic system, space group P21/c with a = 10.4454(7), b = 12.2214(8), c = 10.0818(7) ?, b = 102.284(7), V = 1257.56(15) ?~3, Dc = 2.325 g/cm^3, Mr = 880.24, Z = 2, F(000) = 880, μ = 2.859 mm^-1, the final R = 0.0426 and wR = 0.0822 for 5526 observed reflections with I > 2σ(I). Structural analyses indicate that 1 exhibits a three-dimensional(3 D) pillared-layer framework with triazolate extended Co4^Ⅱ layers supported by rigid L^4- connectors. Magnetically, complex 1 displays strong spin-frustrated antiferromagnetism due to the triangular magnetic lattice and cooperative antiferromagnetic couplings mediated by quadruple heterobridges.