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 .     

Tuning the Topological Net via the Metal Ion‐Driven Assembly of Two ZnII / CdII Coordination Polymers: Syntheses,Crystal Structures,and Luminescent Properties

The coordination polymers {[Zn₂(HIDC)₂(tib)] · H₂O}_n ( 1 ) and {[Cd(HIDC)(tib)] · H₂O}_n ( 2 ) [H₃IDC = 1H‐imidazole‐4, 5‐dicarboxylic acid, tib = 1, 3,5,‐tris(1‐imidazolyl) benzene] were obtained under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy. Complex 1 exhibits a two‐dimensional layer structure with a 6³‐hcb topology. Complex 2 has a three‐dimensional structure with a pcu topology. It is shown that the carboxylate ligand can bear diverse structures regulated by metal ions. Additionally, the photoluminescence behaviors of complexes 1 and 2 are discussed.     

Syntheses,Crystal Structures,and Luminescent Properties of ZnII/CdII Coordination Polymers with Different Interpenetrating Networks

Zn^II and Cd^II coordination polymers with dicarboxylate and imidazole‐containing ligands, namely, [Cd (2,3‐PDC)(L)]_n ( 1 ) and {[Zn(3,4‐PDC) (L)_0.5] · H₂O}_n ( 2 ), [2,3‐H₂PDC = 2,3‐pyridine dicarboxylate, 3,4‐H₂PDC = 3,4‐pyridine dicarboxylate, and L = 1,4‐bis(2‐methylimidazol‐3‐ium‐1‐yl)biphenyl], were prepared and characterized by elemental analysis, IR spectroscopy, and X‐ray diffraction. Complex 1 shows a three‐dimensional (3D) structure with threefold interpenetrating diamond topology. Complex 2 features a 3D framework with twofold interpenetrating dmc topology. Moreover, the luminescent properties of complexes 1 and 2 were also investigated.     

Syntheses,Crystal Structures and Photophysical Properties of a Series of Cadmium(II) Coordination Polymers

Three cadmium(II) coordination polymers [Cd(NA)₂(H₂O)₂]_n ( 1 ), {[Cd(NA)(phen)(NO₃)]·(H₂O)_1/2}_n ( 2 ), {[Cd(NA)(CH₃C₆H₄COO)(H₂O)₂]·(CH₃C₆H₄COOH)}_n ( 3 ) (HNA = nicotinic acid, phen = 1, 10‐phenanthroline) have been synthesized by hydrothermal method. Their single‐crystal structures were determined by X‐ray diffractometry. The absorption, excitation and emission spectra were investigated and all the complexes emit strong fluorescence: λ^em_max = 544 nm (λ^ex = 492 nm), 1 ; λ^em_max = 466 nm (λ^ex = 393 nm), 2 ; λ^em_max = 430 nm (λ^ex = 313 nm), 3 . At room temperature in the solid state the fluorescence lifetimes of the complexes were investigated and the relationships between the spectra were discussed as well as the connections of luminescence and crystal structures.     

两种异金属链状配位聚合物的合成和晶体结构

在甲醇溶液中,将K2NiL·H2O和M(OAC)2(M = Co,Zn)按1:1的摩尔比进行组装反应,得到了镍、钴和镍、锌两种异金属一维链状配位聚合物,其化学组成分别为{[Ni2Co2L2(H2O)2]·CH3OH·3H2O}n（1）和{[Ni2Zn2L2 (H2O)2]·2CH3OH·H2O}n（2）,（H4L=2-羟基-3-[(E)-({2-(2-羟基苯甲酰胺基)乙基}亚氨基)甲基]苯甲酸,OAC- = CH3COO-）。通过IR谱,元素分析的方法对其进行了表征,利用X-射线单晶衍射方法对其晶体结构进行了测定,结构分析表明：它们都是由不对称四核单元组成链状配位聚合物。     

Solvothermal Syntheses,Crystal Structures,and Luminescent Properties of Two Coordination Polymers with Different Interpenetrated Diamond Topology

Two coordination polymers, namely, {[Zn(bpea) (bmp)] · H₂O}_n ( 1 ) and {[Ni(bpea)(bimb)] · DMF}_n ( 2 ) [H₂bpea = biphenylethene‐4,4′‐dicarboxylate, bmp = 1,4‐bis(2‐methylimidazol‐3‐ium‐1‐yl)biphenyl and bimb = 1,4‐bis(1‐imidazol‐yl)‐2,5‐dimethyl benzene], were synthesized under solvothermal conditions with mixed organic ligands. Single crystal X‐ray diffraction reveals that complex 1 features a three‐dimensional (3D) structure with a sixfold interpenetrating dia net. Complex 2 shows a 3D fivefold interpenetrating dia topology. Furthermore, the solid state luminescent properties of complexes 1 and 2 were investigated at room temperature.     

Syntheses and Structures of Coordination Polymers Constructed by Semi‐Rigid Bicarboxylic Acid Ligands

The complexes [Co(L¹)(mpy)] ( 1 ), [Ni(L¹)(mpy)] ( 2 ), [Co(L¹)(tbpy)] · 2H₂O ( 3 ), [Ni₂(L¹)₂(tbpy)₂] · 5H₂O ( 4 ), [Mn₂(L¹)₂(tbpy)₂] · 3H₂O ( 5 ), [Mn(L¹)(biim‐3)] ( 6 ), [Ni₂(L¹)₂(btb)₂(H₂O)] · 2H₂O ( 7 ), [Cu(L²)(mpy)] · 7H₂O ( 8 ), [Co(L²)(tbpy)(H₂O)] ( 9 ), [Ni(L²)(tbpy)(H₂O)] · H₂O ( 10 ), [Cu(L²)(bib)] · 2H₂O ( 11 ), and [Cu(L²)(btb)] · 2H₂O ( 12 ) [H₂L¹ = (3‐carboxyl‐phenyl)‐(4‐(2′‐carboxyl‐phenyl)‐benzyl)ether, H₂L² = 3‐carboxy‐1‐(4′‐carboxybenzyl)‐2‐oxidopyridinium, mpy = 2‐(4‐(4′‐methylphenyl)‐6‐(pyrindin‐2‐yl)pyridin‐2‐yl)pyridine), tbpy = 2‐(4‐(4′‐tert‐butylphenyl)‐6‐(pyrindin‐2‐yl)pyridin‐2‐yl)pyridine), biim‐3 = 1,3‐bis(imidazol‐1′‐yl)propane, btb = 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene, bib = 1,4‐bis(imidazol‐1′‐ylmethyl)benzene] were synthesized. Compounds 1 – 6 have similar 1D chain structures, which are further linked by π–π interactions to generate supramolecular double chains for 1 and 2 , and supramolecular layers for 3 – 6 . Compound 7 displays a 3D 6‐connected framework with (4⁴ · 6¹¹) topology. Compound 8 features a monomolecular structure, which is further linked by hydrogen bonds between the lattice water molecules and carboxylate oxygen atoms of L² anions to form a 2D supramolecular layer. The monomolecular structures of 9 and 10 are connected by hydrogen bonds and π–π interactions simultaneously to generate supramolecular layers. Compounds 11 and 12 show layer structures.     

Tuning Structural Topologies of Two Cadmium(II) Coordination Polymers via Isomeric Dipyridyl Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Abstract. Two new coordination polymers {[Cd₂(BDC)₂(3‐bpmp)(H₂O)₂] · 2H₂O}_n ( 1 ) and [Cd₂(BDC)₂(4‐bpmp)]_n ( 2 ) [H₂BDC = 5‐hydroxy‐isophthalic acid, 3‐bpmp = 1,4‐bis(3‐pyridylmethy)piperazine, and 4‐bpmp = 1,4‐bis(4‐pyridylmethy) piperazine] were synthesized via hydrothermal synthesis, and further characterized by IR spectroscopy, elemental analysis, XRD, and X‐ray crystallography. Complex 1 shows a two‐dimensional (4,4) sql topology and complex 2 features an 8‐connected hex topology. Moreover, the luminescent properties of complexes 1 and 2 were investigated in the solid state at room temperature.     

Syntheses,Structures, and Photoluminescence of Two Three‐dimensional Cadmium Coordination Polymers with Benzene­dicarboxylate Ligands

Two cadmium(II) coordination polymers, namely, [Cd₃(m‐phth)₂(atz)₂]_n ( 1 ) (m‐phth = m‐phthalate and atz = 3‐amino‐1,2,4‐triazolate) and [Cd(atphth)(H₂O)]_n ( 2 ) (atphth = 2‐aminoterephthalate), were synthesized and structurally characterized. Compound 1 features a three‐dimensional (3D) pillared framework based on two‐dimensional (2D) cadmium‐benzenedicarboxylate ladders pillared by the triazolate ligands. Compound 2 has a 3D framework constructed from 2D cadmium‐benzenedicarboxylate layers, which are further linked by Cd–N bonds between the cadmium ions and amino groups of the atphth^2– ligands of the adjacent layers to form the final 3D structure. Compounds 1 and 2 exhibit solid‐state photoluminescence with emission maxima at 448 and 470 nm, respectively.     

Synthesis,Crystal Structures,and Fluorescent Properties of Two ZnII/CdII Coordination Polymers Constructed from Isomeric Ligands

The d¹⁰ coordination polymers (CPs), [Zn(L₁)(OH)]_n ( 1 ) and [Cd(L₂)₂]_n ( 2 ) were obtained from isomeric ligands 3‐(6‐aminpyridinium‐3‐yl) benzoic acid (L₁) and 4‐(6‐aminpyridinium‐3‐yl) benzoic acid (L₂), and characterized by elemental analyses, IR spectroscopy, single‐crystal and powder X‐ray diffraction. In compound 1 , a spiral chain structure connected by μ₂‐OH^– and the Zn^II ions, which are further linked by the L₁ ligands to give atwo‐dimensional layered structure. Classical hydrogen‐bonding interactions (O ··· H–N) between adjacent layers result in three‐dimensional supramolecular structure. Compound 2 features a three‐dimensional framework formed by linking [Cd₂(COO)₂] clusters in a bcu net. Thermal stabilities and fluorescent properties of 1 and 2 were also investigated.     

Four Transition Metal Coordination Polymers based on an Aromatic Multi‐carboxylic Acid as Ligand: Syntheses,Crystal Structures,and Fluorescent/Magnetic Properties

Four compounds, namely, [Zn(H₂L)₂ · 4H₂O] ( 1 ), [Cu(HL) · (H₂O)] · H₂O ( 2 ), [Ni₃L₂(bpy)₂ · 12H₂O] · 4H₂O ( 3 ), and [Co₃L₂(bpy)₂ · 12H₂O] · 4H₂O ( 4 ) [H₃L = 4, 4′‐[(5‐carboxy‐1, 3‐phenylene)bis(oxy)]dibenzoic acid], were synthesized under solvothermal conditions by employing a semi‐rigid aromatic multi‐carboxylic acid ligand (H₃L) and ancillary nitrogen ligand (bpy = 4, 4′‐bipyridine). X‐ray diffraction studies revealed that complexes 1 , 3 , and 4 show zero‐dimensional (0D) structures, which were further extended to distinct 3D supramolecular nets by extensive hydrogen‐bond interactions. However, in compound 2 , 1D chains of square‐shaped pores were linked together by HL^2– ligands to generate a 2D porous layer along the ac plane. Comparison of the structures indicated that not only the conformation of the functional ligand, but also the ancillary ligand helped in structural determination of the compounds. Compound 1 exhibited solid fluorescence emission originating from an intraligand π→π* transition. Magnetic susceptibility measurements demonstrated that compound 2 exhibited antiferromagnetic coupling between adjacent copper(II) ions, with the corresponding J values of –141.84 cm^–1. Furthermore, the thermal behaviors of the complexes 1 – 4 were studied by thermogravimetric analysis.     

Syntheses,Structures, and Thermal Reactivity of New ZnII and CdII Thio‐ and Selenocyanato Coordination Compounds

Reaction of Zn^II and Cd^II thiocyanate or selenocyanate with pyrazine leads to the formation of new Zn^II and Cd^II coordination compounds. The structures of [Zn(NCSe)₂(pyrazine)₂]_n ( 1A ), [Cd(NCS)₂(pyrazine)₂]_n ( 2A ) and [Cd(NCSe)₂(pyrazine)₂]_n ( 3A ) consist of octahedrally coordinated metal cations which are surrounded by two terminal N‐bonded anions and two μ₂‐bridging pyrazine molecules. The metal cations are connected via the pyrazine ligands into layers, which are further linked by weak intermolecular S···S respectively Se···Se interactions. Investigations on the thermal degradation behavior of 1A , 2A , and 3A using simultaneous differential thermoanalysis and thermogravimetry as well as X‐ray powder diffraction, IR‐ and Raman spectroscopy prove that on heating, the pyrazine‐rich compound 1A decomposes in one step into zinc selenocyanate without the formation of a pyrazine‐deficient intermediate. In contrast, for compounds 2A and 3A a stepwise decomposition is observed, leading to the formation of the pyrazine‐deficient compounds [Cd(NCS)₂(pyrazine)]_n ( 2B‐I and 2B‐II ) and [Cd(NCSe)₂(pyrazine)]_n ( 3B ) as intermediates. The structures and the thermal reactivity are discussed and compared with that of related transition metal thiocyanates and selenocyanates with pyridine as N‐donor ligand.     

Metal Ion Induced Assembly of Two Coordination Polymers with Different Topological Nets: Syntheses,Crystal Structures,and Luminescent Properties

The coordination polymers [Zn₂(NDA)(HNDA)₂(IPT)₂]_n ( 1 ) and [Mn(NDA)(IPT)]_n ( 2 ) [H₂NDA = naphthalene‐1,4‐dicarboxylic acid and IPT = 4′‐(4‐(1H‐imidazol‐1‐yl)phenyl)‐4,2′:6′,4′′‐terpyridine] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction. Complex 1 features a one‐dimensional ladder‐like chain, whereas complex 2 shows a three‐dimensional CdS topology. The different coordination modes for organic ligands and topological nets for complexes 1 and 2 are mainly related with the metal ions.     

Syntheses,Structures, and Luminescent Properties of Two Novel Coordination Polymers with Dipicolinate and Diimidazole Ligands

Two novel coordination polymers, [Zn(dpc)(bmix)_0.5]_n ( 1 ), [Pb(dpc)(bmix)_0.5]_n ( 2 ), [dpc = dipicolinate, bmix = 1,4‐bis(2‐methylimidazole‐1‐ylmethyl)benzene], were hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, TGA, and X‐ray single crystal diffraction. In both complexes, the dipicolinate and bmix ligands act as spacers to link metal ions to give a 2D corrugated (6,3) network of 1 and a 3D microporous framework of 2 , respectively. The difference in the architectures is due to a diverging coordination mode of the carboxylate function. Furthermore, solid state fluorescence properties of the two complexes were investigated at room temperature.     

Solvent‐regulated Assembly of 1D and 2D CdII Coordination Polymers with Tetrafluorophthalate: Syntheses,Structures and Properties

Two new coordination polymers [Cd(1,2‐BDC‐F₄)(H₂O)₂(py)]_n ( 1 ) and {[Cd(1,2‐BDC‐F₄)(H₂O)₂](DMF)}_n ( 2 ) were prepared from the vapor diffusion reactions of Cd^II acetate with tetrafluorophthalic acid (1,2‐H₂BDC‐F₄) under different solvent atmospheres, and structurally characterized by single‐crystal diffraction technique. Both complexes reveal polymeric coordination architectures. Complex 1 is a one‐dimensional (1D) double chain, which crystallizes in the space group, P2₁2₁2₁. In 1 , each Cd^II ion is hexacoordinate by five oxygen atoms from two terminal water and three 1,2‐BDC‐F₄ anions with a μ₃‐bridging mode, as well as one nitrogen donor from one pyridine molecule. Complex 2 is a two‐dimensional (2D) layered network, which crystallizes in the P\bar{1} space group. In 2 , each Cd^II ion is heptacoordinate by seven oxygen atoms from two terminal water and four 1,2‐BDC‐F₄ anions with a μ₄‐bridging mode. The results clearly suggest that the judicious choice of solvent systems does play a critical role in the construction of coordination frameworks with distinct dimensionality and connectivity. Their spectroscopic, thermal, and fluorescence properties have also been investigated.     

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.     

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.     

Two Coordination Polymers based on a Carboxylate‐­functionalized Imidazophenanthroline Derivative Ligand and Phthalic Acid: Syntheses,Structures and Magnetic Properties

Two coordination polymers, [Co₂(Hcpip)₂(phth)]_n · 3n(H₂O) ( 1 ) and [Mn₂(Hcpip)₂(phth)]_n ( 2 ), {H₂cpip = 2‐(2‐carboxyphenyl)imidazo[4,5‐f](1,10)‐ phenanthroline, H₂phth = phthalic acid}, were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. Complex 1 is a 1D chain, in which the dinuclear [Co₂(Hcpip)₂]²⁺ units are linked through (phth)^2– anions. Complex 2 is a 2D layer structure, which is constructed from the 1D chains bridged by (phth)^2– anions. The magnetic properties of 1 and 2 show that the weak ferromagnetic interactions occurred between Co^II ions in 1 and a weak antiferromagnetic interactions exist between Mn^II ions in 2 . These two complexes have good thermal stabilities.     

Syntheses,Crystal Structures,and Photoluminescence of Zinc(II) and Cobalt(II) Coordination Polymers Based on Semiflexible 1,4‐Bis(4‐phenoxy)benzenedicarboxylate

Hydrothermal reactions of Co(NO₃)₂ · 6H₂O and Zn(NO₃)₂ · 6H₂O with 1,4‐bis(4‐phenoxy)benzenedicarboxylic acid (H₂bcpb) resulted in the formation of the coordination polymers [Zn(bcpb)(Py)]_n ( 1 ), and [Co(bcpb)(Py)₂]_n ( 2 ), respectively. Their structures were studied by single‐crystal and powder X‐ray diffraction methods and further characterized by IR spectroscopy, elemental analyses, and thermogravimetric analyses (TGA). Single X‐ray diffraction analyses revealed that complex 1 has a 1D loop chain. Each repeated unit contains two carboxylate ligands and two SBUs (secondary building units), whereas complex 2 has a 2D 4‐connected sql sheet with point symbol (4⁴.6²). The complexes are further expanded to 3D supramolecular structures through non‐covalent bonding interactions. Besides, photoluminescent property of complex 1 was also investigated in the solid state at room temperature.     

Three New Lanthanide Coordination Polymers Built from H2bpdc Ligands: Syntheses,Structures, and Properties

Three new lanthanide‐organic coordination polymers, {[Ln₂(bpdc)₂(H₂O)₆(NO₃)] · NO₃} [Ln = La ( 1 ), Ce ( 2 ), Pr ( 3 )] (H₂bpdc = 2, 2′‐bipyridine‐6, 6′‐dicarboxylic acid) were synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR spectroscopy as well as single‐crystal and powder X‐ray diffraction. Single‐crystal X‐ray diffraction analysis revealed that compounds 1 – 3 are isostructural, composed of two dimensional honeycomb network linked by bpdc ligands. The magnetic property of compound 3 was investigated.