Temperature-controlled Hydrothermal Synthesis of Copper(I or II) Coordination Polymers via a Variety of Copper Coordination Modes

Two 1D coordination polymers Cu₂^I(C₆N₃H₄)₂(1) and Cu^II(C₆N₃H₄)₂·H₂O(2) based on benzotriazole(Bta) were hydrothermally synthesized by controlling the crystallization temperature. Single-crystal X-ray diffraction (XRD) analyses reveal that compound 1 is a 1D tubular structure constructed from two types of 1D chains {-Cu-N=N-N-}_n, where the Cu(I) ions adopt linear, triangular, and tetrahedral coordination modes to connect two types of Bta ligands via π-π interaction inside the tubular-like chain. For compound 2, the Cu(II) ions assume a quadrilateral coordination mode linking to the Bta ligands to give 1D straight chains, which stacks through π-π interactions to construct a 2D layer structure. Further characterizations including elemental analyses, infrared IR spectra, thermogravimetric(TG) analyses and luminescence properties have been done.     

Three Novel 1‐H‐Benzimidazole‐5‐Carboxylate‐Based Nickel(II)/Cobalt(II) Coordination Polymers: Synthesis,Crystal Structures,Luminescent, and Magnetic Properties

Three 1H‐benzimidazole‐5‐carboxylate (Hbic^–)‐based coordination polymers, {[Ni(H₂O)(Hbic)₂] · 2H₂O}_n ( 1 ), {[Ni(H₂O)₂(Hbic)₂] · 3H₂O}_n ( 2 ), and {[Co₂(H₂O)₄(Hbic)₄] · 4DMF · 3H₂O}_n ( 3 ) were obtained by reactions of the ligand H₂bic and Ni^II or Co^II salts in the presence of different structure directing molecules. They were structurally characterized by single‐crystal X‐ray diffraction, IR spectra, elemental analysis, thermal stability, luminescent, and magnetic measurements. Structural analysis suggests that the three polymers exhibit a 2D (4, 4) layer for 1 and 1D linear double chains for both 2 and 3 due to the variable binding modes and the specific spatial orientation of the Hbic^– ligand towards the different paramagnetic metal ions, which were further aggregated into different 3D supramolecular architectures by popular hydrogen‐bonding interactions. Weak and comparable antiferromagnetic couplings mediating by Hbic^– bridge are observed between the neighboring spin carriers for 2 and 3 , respectively. Additionally, complexes 1 – 3 also display different luminescence emissions at room temperature due to the ligand‐to‐metal charge transfer.     

Hydrothermal Synthesis,Structural Characterization,Magnetic and Photoelectric Properties of Two Cobalt(II) Coordination Polymers

Two cobalt(II) coordination polymers, {[Co(μ‐4,4′‐bipy)(4,4′‐bipy)₂(H₂O)₂]·(OH)₃·(Me₄N)·4,4′‐bipy·4H₂O}_n ( 1 ) and {[Co(μ‐4,4′‐bipy)(H₂O)₄]·suc·4H₂O}_n ( 2 ) (4,4′‐bipy = 4,4′‐bipyridine, suc = succinate dianions), were hydrothermally synthesized and structurally characterized by X‐ray diffraction analysis, UV‐Vis‐NIR, and ICP. The main structure feature common to the both polymers is presence of the infinite linear chains, [Co(μ‐4,4′‐bipy)(4,4′‐bipy)₂(H₂O)₂]_n ( 1 ) and [Co(μ‐4,4′‐bipy)(H₂O)₄]_n ( 2 ), respectively. In 1 , the chains are further linked by the hydrogen‐bond and π‐π stacking interaction, producing extended layer structure. The 4,4′‐bipy molecules in 1 play three different roles. In 2 , the chains are linked into three‐dimensional network structure via complicated hydrogen bonding system. The variable temperature (2.0～300 K) magnetic susceptibility of 1 indicates a tendency of spin‐transition in the temperature range of 110 K to 22 K, which attributes to the transition of high‐spin to low‐spin from Co²⁺(d⁷) ion. Also, the result of surface photovoltage spectroscopy (SPS) reveals that the polymer 1 has significant photoelectric conversion property in the region of 300‐800 nm.     

Multi‐Dimensional Cobalt(II) and Nickel(II) Coordination Polymers

A series of metal coordination polymers, [Co₂(NB)₄(bpp)₂(H₂O)]·H₂O ( 1 ), [Co₂(e,e‐trans‐chdc)(e,a‐cis‐chdc)(bpp)₂] ( 2 ), [Ni(e,e‐trans‐chdc)(bpp)(H₂O)₂] ( 3 ), [Ni₂(PDA)₂(bpp)₂(H₂O)₃]·H₂O ( 4 ), and [Ni‐(mBDC)(bpp)] ( 5 ) (NB = 3‐nitrobenzoate anion; bpp = 4,4′‐trimethylene dipyridine; chdc = cyclohexane‐1,4‐dicarboxylate anion; PDA = 1,4‐phenylenediacetate anion; mBDC = 1,3‐benzene dicarboxylate anion), were synthesized from metal ions and organic mixed‐ligands by hydrothermal reactions. The single crystal structure analysis revealed that 1, 3, and 4 were 2D sheets with bilayer (1 and 4) and 2‐fold interpenetrated layers (3), 2 is a 3D binodal (4,5)‐connected framework, and 5 is a 1D chains. The non‐covalent interactions of H‐bonds and π–π stacking caused this conformation of highly cross‐linked networks. Compounds 1‐5 were further characterized by thermal gravimetric analysis, powder X‐ray diffraction, UV‐vis, infrared, and PL spectroscopy.     

Hydrothermal Synthesis of a 3D Polymeric Cobalt(II) Carboxylate Derivative from 1,2,4,5‐Benzenetetracarbonitrile

The metal‐organic complexes Co₂(terpy)₂(btec)·H₂O 1 (terpy = 2,2′:6′,2″‐terpyridine, btec = 1,2,4,5‐benzenetetracarboxylate) was synthesized by hydrothermal synthesis method, using 1,2,4,5‐benzenetetracarbonitrile, terpy and CoAc₂·4H₂O. Single crystal X‐ray diffraction showed that each btec^4– ligand links four Co^II atoms and each Co^II atom links to two btec^4– ligands forming a 1D double‐chain structure. Furthermore, the chains pack together through short face–face π–π interactions forming a 3D supramolecular structure. Additionally, the magnetic measurements show antiferromagnetic interactions among metal ions for compound 1 .     

Synthesis,Crystal Structure,and Magnetic Properties of a New Coordination Polymer Framework [CoII(4,4′‐bpy)(N3)2]n

A new cobalt(II) coordination polymer containing 4,4′‐bipyridine and azide as bridging ligand, [Co^II(4,4′‐bpy)(N₃)₂]_n ( 1 ) was synthesized under mild hydrothermal conditions and was characterized by single‐crystal X‐ray diffraction studies and magnetic susceptibility measurements. It exhibits an acentric structure, in which cobalt(II) ions are linked through end‐to‐end (EE) azido groups. The 4,4′‐bpy ligands are coordinated on the axial positions of the octahedral environment reinforcing the intermetallic connections and resulting in a network. Circular dichroism spectra of the compound exhibit a maximum negative Cotton effect at 260 nm, which indicates the chiral nature of 1 . Variable temperature magnetic susceptibility measurements in the temperature range 2–300 K reveal the existence of antiferromagnetic couplings in the framework.     

4,4'-二(1-咪唑基)苯硫醚及邻苯二甲酸根构筑的两个配位聚合物的合成、晶体结构及荧光性质

在温和的水热条件下,以4,4'-二(1-咪唑基)苯硫醚(BIDPT)和邻苯二甲酸(H₂pht)为配体,合成了2个配位聚合物{[Zn(BIDPT)(pht)]₂·2H₂O·CH₃OH}_n(1)和{[Cd₅(BIDPT)₄(pht)₅]·H₂O}_n(2),分别用X-射线单晶衍射、元素分析和IR等手段对它们进行了表征。结果表明,配位聚合物1和2为2D层状结构,配位聚合物1属于正交晶系,Pbcn空间群;配位聚合物2属于三斜晶系,P2₁/c空间群。此外还考察了1和2的热稳定性和固体荧光性质。     

4, 4'-二(1-咪唑基)苯硫醚及邻苯二甲酸构筑的两个配位聚合物的合成、晶体结构及荧光性质

在温和的水热条件下,以4,4'-二(1-咪唑基)苯硫醚(BIDPT)和邻苯二甲酸(H₂pht)为配体,合成了2个配位聚合物{[Zn(BIDPT)(pht)]₂·2H₂O·CH₃OH}_n(1)和{[Cd₅(BIDPT)₄(pht)₅]·H₂O}_n(2),分别用X-射线单晶衍射、元素分析和IR等手段对它们进行了表征。结果表明,配位聚合物1和2为2D层状结构,配位聚合物1属于正交晶系,Pbcn空间群;配位聚合物2属于三斜晶系,P2₁/c空间群。此外还考察了1和2的热稳定性和固体荧光性质。     

两个包含联苯三羧酸配体的铜(II)和锰(II)配合物的合成、晶体结构及磁性质

采用水热方法,用联苯三羧酸配体(H3dppa)和4,4′-联吡啶(4,4′-bipy)分别与CuCl_2·2H_2O和MnCl_2·4H_2O反应,合成了一个具有零维双核铜结构的配合物[Cu_2(Hdppa)_2(4,4′-bipy)(H_2O)_4]·4,4′-bipy·6H_2O(1)和一个基于双螺旋链单元的三维配位聚合物{[Mn_3(μ_5-dppa)_2(4,4′-bipy)(H_2O)_2]·4H_2O}_n(2),并对其结构和磁性质进行了研究。结构分析结果表明2个配合物分别属于三斜和单斜晶系,P1和C2/c空间群。配合物1具有零维双核铜结构,而且这些双核铜单元通过O-H…O/N氢键作用进一步形成了三维超分子框架。而配合物2中存在一个双螺旋锰链单元,这些锰链单元又通过配体进一步连接成了三维结构。研究表明,配合物2中相邻锰离子间存在反铁磁相互作用。     

Syntheses,Structures and Magnetic Properties of Two Coordination Polymers Based on 2, 2-Biphenyldicarboxylate Ligand

Two coordination polymers {[Co₃L₃(Me₂NH)₂]·(Me₂NH)}_n(1) and [CuL(bpy)]_n(2)(L=2,2'-biphenyl dicarboxylate ion, bpy=4,4'-bipyridine) were obtained and characterized. Compound 1 was synthesised via solvothermal method, with the L ligands adopting syn-syn-μ₂-η¹:η¹- and μ₂-η²-coordination modes and Co(II) centers being linked to form a 1D coordination chain with trinuclear Co₃ cluster as sub-units. Compound 2 was synthesized at room temperature, with the L ligand chelating the Cu(II) centers to form a 1D chain, which was further linked by the auxiliary 4,4'-bpy ligand to form a 3D coordination network. The results of variable temperature susceptibility studies reveal that there were ferromagnetic and antiferromagnetic interactions between the paramagnetic metal centers in compounds 1 and 2, respectively.     

Solvothermal Syntheses and Magnetic Properties of Two New Coordination Polymers with Mixed Ligands

Two new coordination polymers, [Ni(H₂O)(BDC)(bpp)]_n ( 1 ) and [Co(mBDC)(bpp)]_n ( 2 ) (BDC = 1,4‐benzene dicarboxylate anion; bpp = 4,4′‐trimethylene dipyridine; mBDC = 1,3‐benzene dicarboxylate anion), were synthesized by solvothermal reaction and structurally characterized. Single crystal X‐ray diffraction showed that 1 consists of an inclined interpenetration of 1D nets generating an overall 3D entanglement and compound 2 of 1D chains. The luminescent and magnetic properties of both compounds in the solid state were also investigated. Crystal data: 1 : orthorhombic, Pnna; a = 18.3648(6), b = 13.6854(4), c = 16.2307(5) Å, V = 4079.3(2) ų, and Z = 8. Crystal data: 2 : triclinic, ; a = 8.6966(4), b = 10.1093(4), c = 11.8334(4) Å, α = 68.263(1)°, β = 82.895(1)°, γ = 78.370(1)°, V = 945.16(7) ų, and Z = 2.     

Infinite Coordination Polymers of One‐ and Two‐dimensional Cobalt Acetates

Two coordination polymers of cobalt acetate, [Co₅(O₂CMe)₁₀] ( 1 ) and [Co(O₂CMe)₂(H₂O)] · H₂O ( 2 ), were solvothermally synthesized and characterized by single‐crystal and powder X‐ray diffraction analyses, IR spectroscopy, and elemental analysis. Compound 1 crystallizes in orthorhombic space group Pbcn in two‐dimensional layers, which consist of 12‐membered cobalt rings. Compound 2 crystallizes in monoclinic space group C2/m and exhibits one‐dimensional chains, which are bridged by one water molecule and two acetate ligands in (2.11)‐ and (2.20)‐modes. Preliminary magnetic studies revealed that antiferromagnetic couplings exist in both compounds.     

基于芳香四羧酸构筑的两种配位聚合物的荧光及磁性质（英文）

在溶剂热条件下,基于芳香四羧酸合成了2种新颖的配位聚合物:{[Zn2(tptc)(1,4-bimb)2]·H2O}n(1)和{[Ni(tptc)0.5(1,2-bimb)(H2O)]·H2O}n(2),其中,tptc为对-三联苯-3,3″,5,5″-四羧酸,1,4-bimb为1,4-二(咪唑-1-亚甲基)苯,1,2-bimb为1,2-二(咪唑-1-亚甲基)苯。结构分析表明,1为三维结构,拓扑符号为(86);2为二维层状网络,通过氢键相互作用进一步扩展为三维超分子结构。此外,我们还研究了1对阳离子、阴离子的荧光感应以及2的磁性质。     

三维银配位聚合物[Ag3(IN)2(CF3COO)]的水热合成与晶体结构

本文在水热条件下, 通过4-氰基吡啶发生原位水解得到异烟酸, 将其与AgCF3CO2作用合成了新型银配位聚合物, 并通过元素分析和X射线单晶衍射分析等手段对其结构进行了表征.     

Synthesis,Characterization, and Magnetic Properties of Novel Cobalt(II) and Copper(II) Complexes with 5‐(Isonicotinamido)isophthalate Ligand

Two new complexes, {[Co(INAIP) · H₂O] · 2H₂O}_n ( 1 ), and {[Cu(INAIP)] · H₂O}_n ( 2 ) [H₂INAIP = 5‐(isonicotinamido)isophthalic acid] were synthesized under hydrothermal conditions, and characterized by single‐crystal X‐ray structure determination, thermogravimetric analysis, X‐ray powder diffraction, and magnetic studies. In complex 1 both Co^II atoms and INAIP^2– ligands act as four‐connected node, whereas in 2 both Cu^II atoms and INAIP^2– ligands act as three‐connected node.     

Syntheses,Structures, and Magnetic Properties of Two Novel Cobalt(II) Coordination Polymers Constructed from Pyridine‐2,6‐dicarboxylic Acid N‐oxide (PDCO)

Two new cobalt(II) coordination polymers, [Co(PDCO)(H₂O)₂]_n ( 1 ) and [Co(PDCO)(bix)(2H₂O)₂·H₂O]_n ( 2 ) ( PDCO= pyridine‐2,6‐dicarboxylic acid N‐oxide, bix = 1,4‐bis(imidazol‐1‐ylmethyl)‐benzene) have been synthesized under hydrothermal conditions. Single‐crystal X‐ray analyses show that compound 1 is a 1D helical chainlike structure with 4₁ screw axes parallel to the crystallographic c‐axis and interchain hydrogen‐bonding interactions further result in a 3D framework; for compound 2 , each bix ligand connects two Co1 atoms (or two Co2 atoms) to give a zigzag chain structure and these 1D chains are connected by offset face‐to‐face π···π and hydrogen bond interactions to generate a 3D architecture. The thermogravimetric analyses were investigated for 1 and 2 . The determination of variable temperature magnetic susceptibilities indicates an antiferromagnetic interaction between the metal atoms for 1 and 2 .     

Hydrothermal Syntheses,Crystal Structures,and Luminescent Properties of Two Zinc(II) Coordination Polymers

Two zinc(II) compounds, namely [Zn₅(AmTAZ)₆(OH)₂]_n · 2n(NO₃) · 6n(H₂O) ( 1 ) and [Zn₃(AmTAZ)₂(mal)₂]_n ( 2 ) (HAmTAZ = 3‐amino‐1,2,4‐triazole, H₂mal = malonic acid), were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, and X‐ray diffraction. Single crystal X‐ray diffraction analysis reveals that compound 1 features a 3D framework with dodecahedral cages occupied by free nitrate ions and lattice water molecules and can be reduced into a (4, 8)‐connected flu topological network. Compound 2 features a 3D framework based on two different 1D chains. Moreover, the thermal stabilities and luminescent properties of compounds 1 and 2 were investigated.     

Stable Triarylmethyl Radicals and Cobalt(II) Ions Based 1D/2D Coordination Polymers

The incorporation of organic radicals into coordination polymers was considered as a promising strategy to promote metal-ligand exchange interactions, but there are only a very limited number of stable organic radical-based ligands that can serve well such a purpose. Herein, we report two new tris(2,4,6-trichlorophenyl)methyl (TTM) radical-based ligands L1 and L2 with two and three imidazole substituents, respectively. The imidazole unit serves as a coordination site and it can also stabilize the TTM radical by intramolecular donor–acceptor interaction. Coordination of L1 and L2 with cobalt(II) ions gave the corresponding one- ( CoCP - 1 ) and two-dimensional ( CoCP - 2 ) coordination polymers, the structures of which were confirmed by X-ray crystallographic analysis. Magnetic measurements and theoretical calculations suggest antiferromagnetic coupling between the paramagnetic cobalt(II) ions and the radical ligands. Our study provides a rational design for stable organic radical-based ligands and further demonstrated the feasibility of a metal–radical approach toward magnetic materials.     

基于双咪唑基柔性配体的一维链状铜(Ⅰ)、钴(Ⅱ)配合物的合成、结构和性质

柔性配体1,4-二亚甲基咪唑-2,3,5,6-四甲基苯(p-bitmb)与不同金属盐发生水热反应,得到两个新的配位聚合物{[Cu(Ⅰ)2Cl(p-bitmb)2][Cu(Ⅰ)Cl2]·H2O}n(1)和[CoCl2(p-bitmb)]n(2)。用单晶X-射线,元素分析,FTIR,热重分析对两个化合物进行了表征。配合物1和2都具有一维链状结构,但1中的一维链进一步通过π-π堆积和氢键作用拓展成二维超分子结构。值得注意的是配合物1合成过程中的Cu(Ⅱ)被还原为Cu(Ⅰ),推测是由于在高的合成温度下被具有还原性的咪唑环还原引起的。     

Syntheses,Crystal Structures,and Magnetic Properties of Two Cobalt Coordination Polymers Constructed From 1,3‐Bis(2,4‐dicarboxyphenyl) Benzene and Bis(imidazole) Linkers

Abstract. The 3D cobalt(II) coordination polymers [Co_1.5(HDDB)(1,4‐bib)_1.5(H₂O)]_n ( 1 ), and {[Co₂(DDB)(1,3‐bib)₂(μ₂‐H₂O)] · H₂O}_n ( 2 ) were assembled by mixed‐ligand synthetic strategy [H₄DDB = 1,3‐bis(2,4‐dicarboxyphenyl) benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and 1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene]. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X‐ray diffraction analysis reveals that complex 1 is an interestingly 3D (3,3.6)‐connected (6³)₄(6⁵ · 8⁸ · 10²) net, and complex 2 is an unprecedented dinuclear [Co₂(COO)(μ₂‐H₂O)] SBUs based 3D (3,6)‐connected (3 · 6 · 7)(3² · 4³ · 5⁴ · 6³ · 7 · 8²) net. Additionally, the magnetic properties of 2 were investigated.