Synthesis and Luminescent Properties of Two Zinc(II) Coordination Polymers Constructed by 4‐(Pyridin‐4‐ylmethoxy)benzolic Acid Ligand

Two coordination polymers, namely [Zn(L)Cl] ( 1 ) and [Zn(L)₂] ( 2 ) [L = 4‐(pyridin‐4‐ylmethoxy)benzolic acid] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analyses, powder X‐ray diffraction, and thermogravimetric analysis. Compounds 1 and 2 have a two‐dimensional square‐shaped structure (the dimensions are 15.43 × 15.43 Å for 1 and 12.064 × 15.017 Å for 2 ) with (4⁴ · 6²) topology. Moreover, compounds 1 and 2 exhibit a 3D supramolecular structure made up by strong π–π interactions from the adjacent layers. Furthermore, compounds 1 and 2 show good fluorescence properties in the solid state at room temperature.     

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.     

Substituent Dependent Dimensionality in Luminescent Zinc Isophthalate Coordination Polymers Containing Bis(3‐pyridylmethyl)piperazine

Divalent zinc coordination polymers containing bis(3‐pyridylmethyl)piperazine (3‐bpmp) and isophthalate ligands have been hydrothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction. {[Zn(ip)(H3‐bpmp)]ClO₄·4H₂O}_n ( 1 , ip = isophthalate) has twofold parallel interpenetrated (4,4) grid cationic coordination polymer nets, with unligated perchlorate ions and intriguing infinite water molecule chains. {[Zn₂(NO₂ip)₃(H₂3‐bpmp)(H₂O)₅]·3H₂O}_n ( 2 , NO₂ip = 5‐nitroisophthalate) exhibits a supramolecular lattice built from 1D chain motifs, revealing a significant dependence of topology on the steric bulk of the dicarboxylate ligand. Luminescent properties for 1 and 2 are also reported.     

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.     

Solvothermal Synthesis and Crystal Structure of One‐Dimensional Chains of Anhydrous Zinc and Magnesium Formate

Reaction of the zinc or magnesium formate dihydrates in formic acid under solvothermal conditions results in the formation of single crystals of the anhydrous metal(II) formates β‐Zn(OOCH)₂ and β‐Mg(OOCH)₂. Both structures form one‐dimensional chains of μ‐oxygen‐bridged metal atoms. Single crystal diffraction studies reveal that β‐zinc formate represents the first structure in which chains of oxygen‐bridged metal atoms are connected by alternating single, double and triple oxygen atom bridges resulting in the first observation of corner, edge and face sharing coordination octahedra within a single chain. Polycrystalline material can be obtained by dehydration reaction of zinc formate dihydrate. β‐magnesium formate is the crystalline product that is obtained by annealing the amorphous intermediate phase after dehydration of magnesium formate dihydrate.     

Solvent Molecule Controlled Zinc(II) Metal‐Organic Frameworks with Different Topology

Two zinc(II) coordination polymers, namely [Zn₂(bptc)(DMF)₂(H₂O)]_n ( 1 ) and [Zn(bptc)_0.5(DMA)]_n ( 2 ) (H₄bptc = biphenyl‐3,3′,5,5′‐tetracarboxylic acid, DMF = N,N′‐dimethylformamide, DMA = N,N′‐dimethylacetamide), were obtained under solvothermal conditions by varying the reaction solvents. Single crystal X‐ray diffraction analyses revealed that compound 1 features a 3D PtS type framework based on dinuclear [Zn₂O(COO)₂] subunits and compound 2 features a 3D lvt type framework based on paddle‐wheel shaped [Zn₂(COO)₄] subunits. Moreover, the luminescent and thermal stabilities of these two compounds were investigated.     

Synthesis,Characterization, and Luminescence of Two New Zinc(II) Coordination Polymers Constructed by 5‐(4‐Carboxybenzyloxy)Isophthalic Acid Ligand

Two coordination polymers, namely Zn(HL)(4,4′‐bpy)_1.5 ( 1 ), [Zn₃(L)₂(BIMB)₂] · 5H₂O ( 2 ) [H₃L = 5‐(4‐carboxybenzyloxy)isophthalic acid, 4,4′‐bpy = 4,4′‐bipyridine, BIMB = 1,4‐bis(1H‐imidazol‐1‐yl)benzene] were synthesized under hydrothermal conditions. Their structures are determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and thermogravimetric (TG) analyses. Complex 1 features a 2D 4‐connected network. Complex 2 is a 3D twofold interpenetrating (3,4,6)‐connected net. In addition, the luminescent properties for 1 and 2 were studied in the solid state at room temperature.     

基于半刚性乳酸衍生物的单一手性配位聚合物的合成、 结构与性质

在溶剂热反应条件下, 用预先合成的乳酸衍生物(R)-H₂CBA和(S)-H₂CBA分别与含氮辅助配体(E)-1,2-二(4-吡啶基)乙烯(DPEE)和1,4-二(1H-咪唑-1-基)苯(1,4-DIB)组合, 制备出2对不同结构的单一手性配位聚合物[Cd₂((R)-CBA)₂(DPEE)(H₂O)₂]_n(1-D), [Cd₂((S)- CBA)₂(DPEE)(H₂O)₂]_n(1-L), [Cd((R)-CBA)(1,4-DIB)]·H₂O(2-D)和[Cd((S)-CBA)(1,4-DIB)]·H₂O(2-L). 其中1-D和1-L是由梯形Cd-CBA链和DPEE配体连接成的二维框架结构; 而2-D和2-L是三维超分子框架结构, 包含3种不同类型的对映手性螺旋链. 对上述化合物进行了粉末X射线衍射、 热重分析和圆二色谱分析, 并对其荧光性质进行了讨论.     

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.     

Crystal Structures and Luminescent Properties of Two Zinc(II) Coordination Compounds with a β‐Diketonate Derivative Ligand

The β‐diketonate derivative ligand [H₂L = 6‐(3‐hydroxy‐1‐oxo‐3‐pyrryl‐2‐propen‐1‐yl)‐2‐pyridinecarboxylic acid] and its zinc(II) coordination complexes, [Zn(H₂L)Cl₂] · (EtOH)(H₂O) ( 1 ) and [Zn₄(L)₄(H₂O)₂] · 5H₂O ( 2 ), were prepared and characterized by elemental analysis, IR and NMR spectroscopy, and single‐crystal X‐ray diffraction. Complex 1 is a mononuclear structure. Complex 2 is a [2 × 2] grid tetranuclear structure. The luminescent properties of the free ligand H₂L and complexes 1 and 2 in methanol solution were studied.     

A New Zinc(II) Coordination Polymer with a Threefold‐Interpenetrating Diamondoid Net: Synthesis,Crystal Structure and Luminescent Property

The three‐dimensional (3D) coordination polymer, [Zn(dpa)(bib)]_n ( 1 ) [H₂dap = diaphonic acid and bib = 1,4‐bis(imidazol‐1‐yl)benzene], was prepared by hydrothermal synthesis and characterized by single‐crystal X‐ray diffraction, FT‐IR spectroscopy, XRPD, and elemental analysis. Crystal structure determination revealed that complex 1 shows a threefold diamond topological net. Furthermore, the solid‐state luminescent property of [Zn(dpa)(bib)]_n was investigated.     

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.     

Two Pairs of Homochiral Coordination Polymers with Helices Based on Semi‐rigid Lactic Acid Ligands

Utilizing semirigid lactic acid derivatives (R)‐H₂CBA and (S)‐H₂CBA as chiral ligands, two pair of homochiral coordination polymers formulated as [Zn((R)‐CBA)(1,4‐DIB)] · H₂O ( 1 ‐ D ), [Zn((S)‐CBA)(1,4‐DIB)] · H₂O ( 1 ‐ L ), [Co((R)‐CBA)(1,4‐DIB)] · H₂O ( 2 ‐ D ) and [Co((S)‐CBA)(1,4‐DIB)] · H₂O ( 2 ‐ L ) were prepared under solvothermal reaction condition. Single X‐ray diffraction study reveals that all the complexes are comprised of three kinds of helical chains, which are constructed by corresponding metal ions, CBA^2– ligands, and/or 1,4‐DIB ligands. Moreover, some physical characteristics, such as PXRD, thermal stabilities, solid‐state circular dichroism (CD), luminescent and magnetic properties are also investigated.     

Synthesis,Crystal Structures and Properties of Two New ­Coordination Polymers Constructed from in situ‐generated Pyridyl‐dicarboxylic Acid Ligands

Two novel coordination polymers [Mn₃(EPDA)₂(H₂O)₈ · (ENA) · (ClO₄) · 0.5(HClO₄) · (CH₃OH) · 2(H₂O)]_n ( 1 ) and[Zn(EPDA)(H₂O)]_n ( 2 ) (EPDA = 5‐ethylpyridine‐2, 3‐dicarboxylic acid, ENA = 5‐ethylnicotinate acid) were synthesized and characterized by IR and UV/Vis spectroscopy, elemental analysis, PXRD, TGA, photoluminescence, and single‐crystal X‐ray diffraction. Organic EPDA^2– and ENA^– anions, the decomposition products of ENA‐Pmmi by removing the –Pmmi group under in situ solvothermal conditions, were obtained by performing the reactions of ENA‐Pmmi with Mn^II or Zn^II perchlorate. In complex 1 , the Mn^II ions were bridged by μ₄‐EPDA^2– anions to give a 2D positively charged layer, and the free ENA^– anion and solvent molecules are filled into the gap between the layers through hydrogen bonding interactions to form a sandwich structure. In compound 2 , the μ₃‐EPDA^2– anions bridge divalent Zn²⁺ ions to form a 1D chain, and the ENA^– anions are not involved in stacking interactions but left in the residual solution. In addition, the ENA‐Imoi instead of ENA‐Pmmi, was selected to further investigate this reaction (ENA‐Pmmi and ENA‐Imoi are imazethapyr homologues), and the same experimental results could be obtained.     

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,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 .     

Crystal Structures and Photoluminescence Properties of Zinc(II) and Cadmium(II) Coordination Polymers with “Y”‐Shaped Ligands

Three Zn^II and Cd^II complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L₁)(2,2′‐bpy)₂(H₂O)] · 2H₂O ( 1 ), [Zn(L₁)(bpp)(H₂O)] ( 2 ), and [Cd(L₁)(H₂O)] · H₂O ( 3 ) [H₂L₁ = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.8²). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated.     

Two Zinc(II) Coordination Polymers Based on the Ligand 1, 4‐Bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene: Syntheses,Crystal Structures and Properties

Two coordination polymers (CPs), {[Zn₂(BMB)(5‐AIPA)₂] · 2H₂O}_n( 1 ) and [Zn(BMB)(5‐NIPA)]_n( 2 ) {BMB = 1, 4‐bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene, 5‐AIPA = 5‐aminoisophthalic acid, 5‐NIPA = 5‐nitroisophthalic acid}, were synthesized under hydrothermal conditions. Compound 1 displays a 2D double‐layer structure, which is packed into a 3D supramolecule by interlayer hydrogen bonds and π–π stacking interactions. Compound 2 displays a threefold interpenetrating 3D network, which is composed of left‐handed helical chains and two types of meso‐helical chains along different directions.     

Synthesis,Structures, and Photoluminescence Properties of Five Novel Zinc(II) and Cadmium(II) Coordination Polymers based on Different Zwitterionic Pyridine Ligands

A series of five new Zn^II and Cd^II mixed‐ligand coordination polymers, namely, {[Zn(L₁)(4,4′‐bpy)] · (ClO₄) · 2H₂O} ( 1 ), {[Zn(L₂)(4,4′‐bpy)_0.5] · (ClO₄)} ( 2 ), {[Zn(L₃)(4,4′‐bpy)] · (NO₃) · 2H₂O} ( 3 ), {[Cd(L₄)(4,4′‐bpy)_0.5(NO₃)] · 5H₂O} ( 4 ), and {[Zn(L₄)(4,4′‐bpy)] · Cl · H₂O} ( 5 ) [4,4′‐bpy = 4,4′‐bipyridine, L₁ = 4‐carboxy‐1‐(4‐carboxybenzyl)pyridin‐1‐ium chloride, L₂ = 3‐carboxy‐1‐(4‐carboxybenzyl)pyridin‐1‐ium chloride, L₃ = 4‐carboxy‐1‐(3‐carboxybenzyl)pyridin‐1‐ium chloride, and L₄ = 3‐carboxy‐1‐(3‐carboxybenzyl)pyridin‐1‐ium chloride], were obtained by the reactions of the 4,4′‐bipyridine with four dicarboxylate zwitterionic pyridine ligands. Single‐crystal X‐ray structural analyses reveal that the five complexes demonstrate different molecular frameworks coming from various coordination modes and flexibilities of different dicarboxylate zwitterionic pyridine ligands and central metal atoms. Mononuclear twofold dinuclear 2D twofold interpenetrating net for 2 , four‐coordinate mononuclear twofold interpenetrating 2D layer for 3 , mononuclear 2D layer arranged in parallel and with large grids for 4 , and twofold trans interpenetrating 2D network for compound 5 . The structural diversities in 1 – 5 indicate that the nature of the ligands and the presence of different metal atoms have a great influence on central metal coordination modes and the structural topologies of the metal‐organic molecular architectures. In addition, π ··· π stacking interactions also play important roles in the final crystal packing and supramolecular frameworks. The powder X‐ray diffraction, elemental analysis, and photoluminescence properties of 1 – 5 were studied, which show that architectures play an important role in emission bands and intensities.