Two New Cadmium(II) Compounds based on Distinct Second Building Subunits: Solvothermal Syntheses,Crystal Structures,and Luminescent Properties

Two cadmium(II) coordination polymers, namely [Cd₃(bpt)₂(DMA)₂]_n ( 1 ) and [Cd₂(bpt)(btz)(DMF)]_n ( 2 ) (H₃bpt = biphenyl‐3,4′,5‐tricarboxylic acid, Hbtz = 1H‐benzotriazole, DMA = N,N‐dimethylacetamide; DMF = N,N‐dimethylformamide), were solvothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction. Compound 1 displays a 3D framework based on trinuclear {Cd₃(COO)₄} subunits and can be simplified into a (4,8)‐connected topological network by viewing bpt^3– ligands and trinuclear {Cd₃(COO)₄} units as 4‐, 8‐connected nodes, respectively. Compound 2 also displays a 3D framework but based on 1D chain subunits controlled by carboxylate groups and btz^– ligands. In addition, the thermal stabilities and luminescent properties of compounds 1 and 2 were also investigated.     

Three Functionalized Zinc(II)/Cobalt(II) Coordination Complexes Demonstrating Fluorescent Sensing Activities towards Fe3+ Ions and Photocatalytic Selectivity for Organic Dyes

Three new zinc(II)/cobalt(II) coordination complexes [Zn(HBTB)(L)_0.5] ( 1 ), [Zn(HCPPA)(L)] ( 2 ), and [Co(HCPPA)(L)] · 2H₂O ( 3 ) [H₃BTB = 1,3,5-tri(4-carboxylphenyl)benzene, H₃CPPA = 5-(4-carboxyl-phenoxy)-isophthalic acid, L = N¹,N⁴-bis(3-pyridyl)naphthaldiamide] were solvothermally synthesized. The structural characterization reveals that complex 1 represents a 3D coordination framework with a binodal 3,4-connected {4.10²}₂{4.10⁵}₂ topology constructed from the 2D [Zn(HBTB)]_n polymeric double-layers and the bidentate L ligands. Complex 2 is a 1D metal-organic chain derived from the dinuclear [Zn₂(HCPPA)₂] loops and [Zn₂(L)₂] loops. Complex 3 possesses a binodal 3,5-connected {4².6}{4³.6.8⁴.10²} topological 2D layered architecture based on the [Co₂(HCPPA)₂] ribbon chains and the bidentate L ligands. For 2 and 3 , their adjacent chains or layers are respectively stacked into 3D supramolecular architectures via the hydrogen bonds. Moreover, the fluorescent and fluorescent sensing activities towards small solvent molecules of coordination complexes 1 and 2 , the photocatalyitc properties of 1 – 3 towards organic dyes were studied.     

Synthesis,structure and photoluminescence of three 2D Cd(II) coordination polymers based on varied dicarboxylate ligand

Three coordination polymers (CPs) based on different dicarboxylic acids and Cd(II), [Cd₃(tpa)₃(DMA)₄] (1), [Cd₂(thpa)₂(DMA)₂·DMA] (2), and [Cd₃(eba)₃(DMA)] (3) (H₂tpa = terephthalic acid, H₂thpa = thiophenedicarboxylic acid, H₂eba?=?(ethene-1,2-diyl)dibenzoic acid, DMA = N,N′-dimethylacetamide), were synthesized under solvothermal conditions. The CPs were characterized by elemental analysis (EA), single-crystal X-ray crystallography, powder X-ray diffraction, infrared spectroscopy (IR), and thermogravimetric analyses. X-ray crystallographic analysis shows that 1 and 3 exhibit a 2D six-connected hxl network based on hourglass-like [Cd₃(COO)₆] SBUs, whereas 2 displays a 2D 4⁴-sql network based on [Cd₄(COO)₈] SBUs. Thermal stabilities and photoluminescence behaviors of the CPs are also discussed.     

Syntheses,Structures, and Luminescent Properties of Two Isostructural 3D CdII Frameworks based on Rigid-flexible Hybrid Ligands

Two isostructural Cd^II frameworks, [Cd₂(MMA)₂(bpy)(H₂O)₂]_n ( 1 ) and [Cd₂(MMA)₂(bpe)(H₂O)₂]_n ( 2 ), were synthesized solvothermally with hybrid flexible methylmalonic acid (H₂MMA) and rigid 4,4'-bipyridine (bpy) or trans-1,2-bis(4-pyridyl)ethylene (bpe) as coligands. Single-crystal X-ray diffraction analyses reveal that complexes 1 and 2 display a three-dimensional (3D) framework structure composed of 2D [Cd(MMA)] layer unit and bpy/bpe linker, and exhibit a (3,4)-connected topological network with Schläfli symbol of {6³}{6⁵.8}. The solid-state luminescent properties were studied, and 1 and 2 show a distinct emission centered at 465 and 531 nm, respectively.     

基于三羧酸构筑的两个金属-有机骨架(MOFs):合成,晶体结构和性质(英文)

以1,3-二(4′-羧基苯氧基)苯甲酸(H3L)为配体与金属盐反应,在水热条件下成功合成了2个金属-有机骨架(MOFs),分别为[Cd2(CH3COO)(L)(H2O)2]n(1)和[Na(H2L)]n(2)。由于H3L配体配位模式的不同,配合物表现出不同的网络结构。单晶结构分析表明,配合物1属于三斜晶系,P1空间群,配合物2属于单斜晶系,C2/c空间群。配合物1中Cd2+离子的次级构筑单元经由L3-连接形成三维网络结构。配合物2是一个5-连接的拓扑网络结构,其拓扑符号为(46·64)。此外,还对配合物1的荧光性能进行了分析。     

基于三羧酸构筑的两个金属-有机骨架(MOFs):合成,晶体结构和性

以1,3-二(4'-羧基苯氧基)苯甲酸(H₃L)为配体与金属盐反应,在水热条件下成功合成了2个金属-有机骨架(MOFs),分别为[Cd₂(CH₃COO)(L)(H₂O)₂]_n (1)和[Na(H₂L)]_n (2).由于H₃L配体配位模式的不同,配合物表现出不同的网络结构.单晶结构分析表明,配合物1属于三斜晶系,P1 空间群,配合物2属于单斜晶系,C2/c空间群.配合物1中Cd₂₊离子的次级构筑单元经由L^3-连接形成三维网络结构.配合物2是一个5-连接的拓扑网络结构,其拓扑符号为(4⁶·6⁴).此外,还对配合物1的荧光性能进行了分析.     

Anion-induced assembly of 2-D Cd(II) complexes with (42·6)(42·63·8) topology based on ferrocenyl dicarboxylate and tripodal ligands

Self-assembly of a flexible tripodal ligand, 1,3,5-tris(1,2,4-triazol-1-ylmethyl)benzene (ttmb) and organometallic carboxylate 1,1'-bis(3-carboxy-1-oxopropyl)-ferrocene (H₂bfcs) with Cd(Ac)₂?·?2H₂O or CdCl₂?·?2.5H₂O yi elds two 2-D binodal (3,4)-connected complexes {[Cd₂(bfcs)(Hbfcs)₂(ttmb)₂]?·?10H₂O} _n (1) and [CdCl(Hbfcs)(ttmb)] _n (2), exhibiting the same topological type (4²?·?6)(4²?·?6³?·?8). Both exhibit a layer structure, which is generated through 1-D undulated ladders connected by organometallic carboxylate, bfcs^2? (in 1), or Cl^? (in 2). Differential pulse voltammetry experiments indicate that half-wave potentials are slightly higher than that of H₂bfcs. Both complexes exhibit similar weak fluorescent emissions at room temperature.     

Synthesis,Structure, and Characterization of a Microporous Metal‐Organic Framework with PtS Topology

The microporous metal‐organic framework Cd₂(ABTC)(H₂O)(DMA)₂ · H₂O · 3DMA ( 1 ) (H₄ABTC = 3, 3′,5, 5′‐azobenzenetetracarboxylic acid; DMA = N,N′‐dimethylacetamide) was prepared by solvothermal reaction and characterized. X‐ray structure analysis revealed that compound 1 is a three‐dimensional (3D) open framework with 2D channels. The topology is based on a PtS net, constructed of 4‐connected rectangular ABTC^4– units with 4‐connected tetrahedral dinuclear Cd₂(CO₂)₄(H₂O)(DMA)₂ secondary building units (SBUs). The solid‐state excitation‐emission spectra showed that the strongest emission peak is at 403 nm upon excitation at λ = 287 nm.     

Syntheses,crystal structures,and photoluminescent properties of two new Cd(II) coordination polymers based on biphenyl-2,2′,4,4′-tetracarboxylate and dipyridyl-containing ligands

Two new Cd(II) coordination polymers, [Cd₂(btc)(dpe)_1.5(H₂O)]_n (1) and [Cd₂(btc)(bpp)(H₂O)]_n (2), were prepared by the hydrothermal reaction of cadmium nitrate with H₄btc (H₄btc = biphenyl-2,2′,4,4′-tetracarboxylic acid) in the presence of 1,2-di(4-pyridyl)ethylene (dpe) and = 1,2-bis(4-pyridyl)propane (bpp), respectively, structurally characterized by single-crystal X-ray diffraction, and further characterized by elemental analysis, IR spectroscopy, and thermogravimetric analysis. In 1, btc^4? connect six Cd²⁺ ions, forming a 3-D (3,3,6)-connected [Cd₂(btc)] net, and further connected by 1-D [Cd(dpe)]_n chains to construct the final (4,5,6)-connected (4².5².6⁵.7)(4³.6².7)(4⁵.5³.6⁴.7².8) net. In 2, a 3-D [Cd₂(btc)] net is also constructed from btc^4? connecting six Cd²⁺ ions, giving a 3-D (3,4,7)-connected network. The overall structure of 2 can be regarded as a (4,4,6)-connected (4⁵.6⁴) (4².5.6².8) (4³.5⁴.6⁷.7) framework with bpp linking adjacent Cd ions. Structural comparisons show that the secondary auxiliary N-donors have important effects on the final structure and properties. Photoluminescent properties of 1 and 2 are also discussed.     

Two new metal-organic frameworks possessing binodal high-connected topologies based on Cd4-clusters and organic ligands

Two new compounds, [Cd₂(bptc)(bpimb)(H₂O)]?·?2H₂O (1) and [Cd₂(bptc)(bpib)]?·?4H₂O (2) (where H₄bptc?=?biphenyl-3,3′,4,4′-tetracarboxylic acid, bpimb?=?1,3-bis((2-(pyridin-2-yl)-1H-imidazol-1-yl)methyl)benzene, bpib?=?1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane), were synthesized by reactions of the corresponding metal salts with H₄bptc and N-containing auxiliary ligands and their structures have been determined by single-crystal X-ray diffraction. Compound 1 is built by Cd₄-clusters which further construct a 3-D (3,8)-connected framework with tfz-d notation; 2, also built by Cd₄-clusters, is a 3-D (4,8)-connected framework with (3²?·?4²?·?5²)(3⁴?·?4⁸?·?5¹²?·?6⁴) topology. In addition, the elemental analyses, infrared spectra, fluorescence, and thermogravimetric analyses for 1 and 2 are discussed.     

Two New Dinuclear MnII Cluster-based Metal-organic Frameworks: Syntheses,Crystal Structures,and Magnetic Properties

Two new dinuclear Mn^II cluster-based metal-organic frameworks, namely [Mn₂(L)(DMPU)₃]_n ( 1 ) and [Mn(L)_0.5(4,4'-bipy)_0.5(H₂O)]_n ( 2 ) (H₄L = biphenyl-3,3',5,5'-tetracarboxylic acid, DMPU = 1,3-dimethyltetrahydropyrimidin-2(1H)-one, 4,4'-bipy = 4,4'-bipyridine), were solvothermally synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and magnetic studies. Compound 1 crystallizes in the monoclinic P2₁/n space group and displays a 3D framework with 4-connected crb/BCT -type topology, and compound 2 crystallizes in the monoclinic C2/c space group and displays a 3D framework with (4,6)-connected sqc422 -type topology. The magnetic studies of compounds 1 and 2 show the presence of weak antiferromagnetic interactions within the dinuclear Mn^II units.     

Metal-ion-dependent,Solvent-mediated Structural Transformation and Simultaneous Partial Transmetalation of an srs Framework into Desulfurization-efficient Co-Cu-HKUST-1

[Co₂(BTC)(Cl)(DMA)₃] ( 1 ) (BTC^3– = benzene-1,3,5-tricarboxylate, DMA = N,N-dimethylacetamide) obtained from the reaction between Co²⁺ and H₃BTC in DMA features a three-dimensional srs framework built of 3-connected {Co₂(COO)₃} as secondary building units and BTC^3– as spacers. When exposed to DMA solution of Cu(NO₃)₂, 1 was progressively transformed into the first heterometallic Co-Cu-HKUST-1 ([Co_0.14Cu_2.86(BTC)₂]) ( 2 ) of such kind via unusually solvent-mediated structural transformation and simultaneous partial transmetalation. While the mechanism for such conversion is proposed based on systematic studies, 2 was revealed to be an equally efficient desulfurization adsorbent as the homometallic Cu-HKUST-1 in removing thiophene (0.142 mmol S per gram of adsorbent). However, when exposed to Zn(NO₃)₂ solution in DMA for longer time, 1 retained its framework with limited metal-ion exchange, resulting in the formation of [Co_1.93Zn_0.07(BTC)(Cl)(DMA)₃] ( 3 ). Possible reasons responsible for the formation of 2 and 3 through different routes could be due to the less solubility and more thermodynamic stability of 2 in comparison with those of 1 , and the different coordination geometries which Co²⁺, Zn²⁺ and Cu²⁺ prefer.     

Hydroxo-Lanthanide Cluster Organic Framework Built by Hexanuclear Cluster Units

A novel hydroxo-lanthanide cluster organic framework, Sm₃L₈(μ ₃-OH)(H₂O)·H₂O (1), derived from the 4-pyridin-4-ylbenzoic acid (HL) has been hydrothermally made and structurally characterized by single crystal X-ray diffraction. Structure analysis shows the hexanuclear Sm₆ cluster unit is composed of inorganic tetranuclear hydroxo [Sm₄(OH)₂]¹⁰⁺ (Sm₄) cluster and dimeric [Sm₂(COO)₄]²⁺ (Sm₂) core. The Sm₆ cluster units are connected by L ligands to form a 2D Ln-based cluster organic framework. From the topological point of view, the layer architecture can be described as 4-connected sql net. Furthermore, the elemental analysis, PXRD, IR and TGA are also studied.     

以5-(6-羧酸-2-萘基)-间苯二羧酸为配体构筑的两个镉的金属-有机骨架化合物的合成、晶体结构及荧光性质

在溶剂热条件下,以不对称三羧酸5-(6-羧酸-2-萘基)-间苯二羧酸(H₃L)为配体合成了2个镉的金属-有机骨架化合物:{[Cd₃L₂(H₂O)₃]·6DMF}_n(1)和{[Cd₃L₂(H₂O)₄]·3DMA}_n(2)。通过X射线单晶衍射,粉末衍射,热重和红外光谱进行了结构表征。结构分析表明,1和2形成3,6-连接的三维结构,其拓扑符号分别为:(4⁵.6⁴.8⁶)(4³)₂和(6¹².8³)(6³)₂。此外,还对2个化合物进行了荧光分析。     

两个基于四面体型配体的镉配合物的合成、晶体结构及性质

用四面体构型的配体四[3-(羧基苯)氧甲基]甲烷(H₄L)与镉离子通过溶剂热法合成了结构不同的配合物[Cd₆L₃(DMA)₃(H₂O)]_n (1)和{[Cd₂L(H₂O)₄]·4H₂O}_n (2)(L=四[3-(羧基苯)氧甲基]甲烷)。化合物1属于三方晶系R3 空间群。每个配体通过4个羧基连接了4个三核镉簇, 每个三核镉簇连接了6个苯甲酸, 形成双节点(4, 6)-连接toc拓扑构型的三维骨架结构。配合物2属于单斜晶系C2/c空间群。每个配体连接了4个镉原子, 仍保持四面体构型。镉原子由羧基沿着b轴连接成一维链, 链与链之间通过配体连接, 且2个相邻配体的苯环之间存在π-π堆积。此外, 对化合物1和2在室温下做了固态紫外和荧光性质的研究。     

Construction of three new metal-organic frameworks with distinct SBUs: trinuclear {Cd3(COO)6} clusters,inorganic -Cd-O-Cd- chains,and heterometallic trinuclear {Cd2Ba(COO)4} clusters

Three metal-organic frameworks (MOFs), [Cd₃(OABDC)₂(e-urea)₄]_n (1), [Cd₃(OABDC)₂(H₂O)₅)]_n (2) and [Cd₂Ba(OABDC)₂(H₂O)₇]_n (3) (H₃OABDC = 5-oxyacetate isophthalic acid, e-urea = 2-imidazolidinone), were prepared using H₃OABDC and metal salts. Single-crystal X-ray diffraction analyses reveal that 1 features a 2-D layered structure constructed from trinuclear {Cd₃(COO)₆} SBUs and represents a (3,6)-connected kgd topology. Compounds 2 and 3 are 3-D inorganic–organic hybrid frameworks; 2 employs infinite inorganic –Cd–O–Cd– chains as SBUs, whereas (3,6)-connected ant-type 3 employs heterometallic trinuclear {Cd₂Ba(COO)₄} clusters as SBUs. The structures of these three compounds indicate that the SBUs play an important role in the construction of MOFs. Moreover, the thermal stabilities and solid-state photoluminescent properties of these three compounds have also been investigated.     

Tetranuclear cluster-based coordination polymer templated by [Ca(H2O)6]2+ cations for the photocatalytic application

A new [Ca(H₂O)₆]²⁺ cations-templated coordination polymer, namely {[Ca(H₂O)₆][Cu₄(btec)₂(μ₃-OH)₂]}_n ( 1 , H₄btec=1,2,4,5-benzenetetracarboxylic acid), has been prepared via the solvothermal reactions of CuCl₂ ? 2H₂O, CaCl₂, and H₄btec. X-ray structural analysis revealed that it features a tetranuclear [Cu₄(COO)₆(μ₃-OH)₂] cluster-based 3D anionic framework with (4,8)-connected scu topology that was further balanced by the isolated [Ca(H₂O)₆]²⁺ cations. The framework of 1 shows high thermostability under air atmosphere. Moreover, such compound shows high photocatalytic activity for the degradation of methyl blue (MB) with the degradation efficiency of 94.5 %, and the possible photocatalytic mechanism was also clarified.     

以5-(6-羧酸-2-萘基)-间苯二羧酸为配体构筑的两个镉的金属-有机骨架化合物的合成、晶体结构及荧光性质

在溶剂热条件下,以不对称三羧酸5-（6-羧酸-2-萘基）-间苯二羧酸（H3L）为配体合成了2个镉的金属-有机骨架化合物:{[Cd₃L₂（H₂O）₃]·6DMF}_n（1）和{[Cd₃L₂（H₂O）₄]·3DMA}_n（2）。通过X射线单晶衍射,粉末衍射,热重和红外光谱进行了结构表征。结构分析表明,1和2形成3,6-连接的三维结构,其拓扑符号分别为:（4⁵.6⁴.8⁶）（4³）₂和(6¹².8³)（6³）₂。此外,还对2个化合物进行了荧光分析。     

两个三维柱层式单一手性配位化合物:合成、结构和性质（英文）

在溶剂热合成条件下得到2个单一手性配位聚合物,即[Cd3((R)-CIA)2(bipy)2.5(H2O)2]·xGuest(1)和[Zn3((R)-CIA)(bmib)2(H2O)2 Cl]·H2O·xGuest(2)((R)-H3CIA=(R)-5-(1-羧基乙氧基)间苯二甲酸,bipy=4,4′-联吡啶,bmib=1,4-双(2-甲基-1H-咪唑-1-基)苯)。X射线单晶结构分析揭示配合物1和2都是柱层式结构的三维框架。从拓扑分析的角度看,配位物1具有(3,3,3,6,6)-连接的网络,拓扑符号为(4.5^2)2(4.8^2)2(42.6^8.8^3.10^2)(4^2.6^8.8^3.9^2)(5.8.9)2,而配合物2是(3,4,4)-连接的网络,拓扑符号为(6·7^2)2(6·7^5)2(6^2·7^4)。此外,对上述配合物的热稳定性、圆二色谱和荧光性质也做了研究。     

Complexes of nickel(II) carboxylates with pyridine and cyclam: crystal structures,mesomorphisms, and thermoelectrical properties

Nickel(II) carboxylates [Ni(CH₃(CH₂)₁₄COO)₂(H₂O)₂] (1) and [Ni(C₆H₅COO)₂(H₂O)₂] (2) were obtained from reactions of NiCl₂·6H₂O with CH₃(CH₂)₁₄COONa and C₆H₅COONa, respectively. Complex 1 reacted with pyridine (pyr) to form [Ni(CH₃(CH₂)₁₄COO)₂(pyr)₂(H₂O)₂] (3) and [Ni₂(μ₂-H₂O)(CH₃(CH₂)₁₄COO)₄(pyr)₄] (4) in the same reaction mixture, and reacted with cyclam to form an ionic complex, [Ni(CH₃(CH₂)₁₄COO)(cyclam)(H₂O)]CH₃(CH₂)₁₄COO·4H₂O (5). In contrast, 2 reacted with cyclam to form [Ni(C₆H₅COO)₂(cyclam)] (6). Finally, 6 reacted with p-(hexadecyloxy)pyridine (L) to form an ionic complex, [Ni(cyclam)(L)₂](C₆H₅COO)₂ (7). Complexes 3–6 were single crystals. All complexes have octahedral Ni(II) center(s) and were magnetic. Complexes with cyclam as co-ligand were more thermally stable than those with pyridine and its derivative, L. Complexes 3 and 4 were mesomorphic after partial loss of water and/or pyridine ligands on heating. The ionic complexes 5 and 7 were not mesomorphic, but showed good thermoelectrical behavior with negative S_e values in CHCl₃ (?0.28 mV K^?1 for 5; -0.39 mV K^?1 for 7) and positive S_e values in C₂H₅OH (+0.25 mV K^?1 for 5; +0.20 mV K^?1 for 7).