Design,synthesis and structure of uranyl coordination polymers from 2-D layer to 3-D network structure

Solvothermal reaction of uranyl acetate and succinic acid in DMF resulted in formation of three uranyl coordination polymers, [(UO₂)₄(μ₂-OH)₇(OH)₆]·2(H₂O)·(H₃O)·4NH₂(CH₃)₂ (1), [(UO₂)(μ₂-OH)(OH)₃]·2NH₂(CH₃)₂] (2), and [(DMF)₂(UO₂)(μ₂-OH)₄(UO₂))] (3). The products were characterized by elemental analysis, IR spectroscopy, X-ray single crystal, and powder diffraction. Structural analysis shows that 1 is a layer, 2 and 3 are 3-D network structures.     

Synthesis,structure, and catalytic bromination of supramolecular oxovanadium complexes containing oxalate

Three supramolecular complexes, [VO(phen)(C₂O₄)(H₂O)]·CH₃OH (1) [(VO)₂(u₂-C₂O₄)(C₂O₄)₂(H₂O)₂]·L·H₂O (2), and [(4,4′-bipyH₂)_0.5]⁺[VO₂(2,6-dipic)]^?·2H₂O (3) (phen?=?1,10-phenanthroline 4,4′-bipy?=?4,4′-bipyridine, 2,6-dipic?=?2,6-pyridinedicarboxylic, L?=?1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene), have been prepared and characterized by elemental analysis, IR, and UV–vis spectroscopy and single-crystal diffraction analysis. Structural analysis shows that the three complexes all contain carboxylate and V=O moiety; vanadium of 1 and 2 are six coordinate with distorted octahedral geometry with N₂O₄ and O₆ donor sets, respectively, while 3 is five coordinate with distorted trigonal bipyramidal geometry with a NO₄ donor set. The complexes exhibit catalytic bromination activity in the single-pot reaction for the conversion of phenol red to bromophenol blue in H₂O–DMF at 30?±?0.5?C with pH 5.8, indicating that they can be considered as functional model vanadium-dependent haloperoxidases. In addition, electrochemical behaviors are also studied.     

Syntheses,crystal structures and antibacterial activities of M(II) benzene-1,2,3-triyltris(oxy)triacetic acid complexes

Four metal(II) complexes with benzene-1,2,3-triyltris(oxy)triacetic acid (H₃L), {[Co_1.5(L)(H₂O)₆]·6H₂O}_n (1), {[Co_1.5(L)(4,4′-bipy)_1.5(H₂O)₄]·4H₂O}_n (2), {[Co(HL)(2,2′-bipy)(H₂O)₂]·1.5H₂O}_n (3), and {[Cu(HL)(phen)(H₂O)₂]·H₂O}_n (4) (4,4′-bipy = 4,4′-bipyridine; 2,2′-bipy = 2,2′-bipyridine; phen = phenanthroline), were prepared and structurally characterized. Complex 2 displays a 1-D structure, while 1, 3, and 4 reveal 0-D structures, which further extend to 3-D supramolecular networks by hydrogen bonding interactions, of which 1 and 4 contain double-helical chains, 2 includes meso-helices, and 3 comprises single-helices. Furthermore, the thermal stabilities and antibacterial activities of the complexes were studied.     

Ten complexes constructed by two reduced Schiff base tetraazamacrocycle ligands: syntheses,structures, magnetic and luminescent properties

Ten new complexes, [Cu₂(L¹)(NO₃)₂]·2H₂O (1), [Cu₄(L¹)₂]·4ClO₄·H₂O (2), [Cu₂(L¹)(H₂O)₂]·(adipate) (3), [Cu₆(L¹)₂(m-bdc)₄]·2DMF·5H₂O (4), [Cu₂(L¹)(Hbtc)]·5H₂O (5), [Cu₂(L¹)(H₂O)₂]·(ntc)·3H₂O (6), [Co₂(L²)]·[Co(MeOH)₄(H₂O)₂] (7), [Co₃(L²)(EtOH)(H₂O)] (8), [Ni₆(L²)₂(H₂O)₄]·H₂O (9) and [Zn₄(L²)(OAc)₂]·0.5H₂O (10), have been synthesized. 1 displays a [Cu₂(L¹)(NO₃)₂] monomolecular structure. 2 shows a supramolecular chain including [Cu₂L¹]²⁺. In 3, two Cu(II) ions are connected by L¹ to form a [Cu₂(L¹)(H₂O)₂]²⁺ cation. In 4, the m-bdc anions bridge Cu(II) ions and L¹ anions to form a layer. Both 5 and 6 display 3-D supramolecular structures. 7 consists of both [Co₂L²]^2? and [Co(MeOH)₄(H₂O)₂]²⁺ units. 8 and 9 show infinite chain structures. In 10, Zn(II) dimers are linked by L² to generate a 3-D framework. The magnetic properties for 4 and 8 and the luminescent property for 10 have been studied.     

Synthesis,crystal structure,and magnetic properties of a linear trinuclear Cu(II) complex

A new linear trinuclear Cu(II) complex, [Cu₃(NTA)₂(4,4′-bpt)₄(H₂O)₂]?·?10H₂O (H₃NTA?=?nitrilotriacetic acid, 4,4′-bpt?=?4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole) (1), was obtained from evaporation of an aqueous solution containing Cu(NO₃)₂?·?6H₂O, 4,4′-bpt, nitrilotriacetic acid (H₃NTA), and NaOH. 1 was characterized using single-crystal X-ray diffraction, IR, and elemental analysis. In the trimer, the three linear copper ions are bridged by two NTA carboxylate groups in a syn–anti conformation and connected by 4,4′-bpt to produce a 1-D array. Temperature-dependent magnetic susceptibilities reveal the presence of weak antiferromagnetic exchange between metal centers.     

Cd(II) MOFs based on cadmium/carboxylate units and 4,4′-bis(benzoimidazol-1-yl)bibenzene: syntheses,structures, and luminescence

Solvothermal reactions of CdCl₂·2.5H₂O with 4,4′-bis(benzoimidazol-1-yl)bibenzene (bimbb) and 1,4-benzenedicarboxylic acid (1,4-H₂bdc), 4,4′-biphenyldicarboxylic acid (4,4′-H₂bpdb), 5-methyl-1,3-benzenedicarboxylic acid (5-Me-1,3-H₂bdc), or 1,3,5-benzenetricarboxylic acid (H₃btc) afforded four 3-D metal–organic frameworks, {[Cd₂(1,4-bdc)₂(bimbb)₂]·H₂O}_n (1), {[Cd₂(4,4′-bpdb)₂(bimbb)(H₂O)₂]} _n (2), [Cd₂(5-Me-1,3-bdc)₂(bimbb)] _n (3), and {[Cd₃(btc)₂(bimbb)(H₂O)₂]·2H₂O} _n (4). Complexes 1–4 were characterized by elemental analysis, IR spectroscopy, powder X-ray powder diffraction, and single-crystal X-ray diffraction. 1 possesses a 3-D framework with 2-D undulated (8,4) layers which are further connected by bimbb pillars. 2 forms a 3-D pillared-layer framework constructed through 2-D undulated (4,4) layers and bimbb pillars. 3 has 1-D ribbons of [Cd₄(5-Me-1,3-bdc)₄] _n which are linked by bimbb to form a 3-D structure. 4 exhibits a 3-D pillared-bilayer framework consisting of (6,3) double-decker [Cd₉(btc)₆(μ-OH₂)₆] _n layers and bimbb pillars. The Schläfli symbols for the four frameworks are (4²·6³·8)(4²·6⁵·8³) (1), (4⁴·6⁶) (2), (4⁴·6²)(4⁶·6⁴) (3), and (6³)(6¹⁰) (4). The photoluminescent properties of 1–4 were also investigated.     

Synthesis and crystal structures of 3D supramolecular compounds: [ M (4,4′-bipy)2(H2O)4] · (4,4′-bipy)2 · (3,5-daba)2 · 8H2O ( M =Zn,Mn)

Two new supramolecular compounds [M(4,4′-bipy)₂ (H₂O)₄] ·?(4,4′-bipy)₂ ·?(3,5-daba)₂ ·?8H₂O (M=Zn(1) or Mn(2), 4,4′-bipy =?4,4′-bipyridine, 3,5-daba =?3,5-diaminobenzoic acid anion) were synthesized and characterized by elemental analysis and X-ray crystal diffraction. In [M(4,4′-bipy)₂(H₂O)₄]²⁺, the M(II) is coordinated by two nitrogen atoms from two 4,4′-bipy molecules and four oxygen atoms from four waters to form an octahedral configuration. There exist uncoordinated 4,4′-bipy molecules, 3,5-diaminobenzolate counterions and water guests in the compounds. The 3D structures of the title supramolecular compounds are constructed by rich hydrogen bonds among [M(4,4′-bipy)₂(H₂O)₄]²⁺, uncoordinated 4,4′-bipy molecules, water molecules and 3,5-daba, containing a diverting hexa-member water ring.     

Syntheses,structures, and properties of supramolecular complexes with bipyridine and amino-Schiff-base derived from salicylaldehyde with glycine

The reactions of stoichiometric amounts of Cu(CH₃COO)₂ · 2H₂O or Ni(CH₃COO)₂ · 2H₂O with KHL (potassium salt of salicylideneglycine) and 4,4′-bipy or 2,2′-bipy ethanol afforded [Cu₂(L)₂(μ-4,4′-bipy)(4,4′-bipy)₂] · 2H₂O (1) (L = salicylideneglycine) and Ni(OAc)₂(2,2′-bipy) (H₂O)₂ (2), respectively. The structure of 1 contains two Cu(II)'s, bridged by 4,4′-bipy; each copper is square pyramidal. Complex 2 contains a Ni(II) in highly distorted octahedral geometry. The two complexes were constructed into 3-D interwoven networks by typical H-bonding (i.e., O?H ··· O and N?H ··· O) and some other intra- or intermolecular weak interactions (i.e., C?H ··· O).     

Supramolecular networks constructed by cationic copper(II) complexes incorporating hybrid water–anionic polymeric assemblies

Two complexes, [Cu₂(TFSA)(2,2′-bpy)₄]?·?TFSA?·?8H₂O (1) and {[Cu(4,4′-bpy)(H₂O)₂]?·?TFSA?·?6H₂O} _n (2) (H₂TFSA?=?tetrafluorosuccinic acid, 2,2′-bpy?=?2,2′-bipyridine, and 4,4′-bpy?=?4,4′-bipyridine), have been synthesized and structurally characterized by X-ray structural analyses. Complex 1 is a binuclear molecule bridged by TFSA ligands; 2 is a 1-D chain bridged by 4,4′-bpy ligands. The asymmetric units of the two complexes are composed of cationic complexes [Cu₂(TFSA)(2,2′-bpy)₄]²⁺ (1) and [Cu(4,4′-bpy)(H₂O)₂]²⁺ (2), free TFSA anion, and independent crystallization water molecules. A unique 2-D hybrid water–TFSA anionic layer by linkage of {[(H₂O)₈(TFSA)]^2?} _n fragments consisting of 1-D T6(0)A2 water tape and TFSA anionic units by hydrogen bonds in 1 was observed. Unique 2-D hybrid water–TFSA anionic layer generated by the linkage of {[(H₂O)₆(TFSA)]^2?} _n fragments consisting of cyclic water tetramers with appended water molecules and TFSA anionic units, and 1-D metal–water tape [Cu–H₂O?···?(H₂O)₆?···?H₂O^?] _n in 2 were found. 3-D supramolecular networks of the two complexes consist of cationic complexes and water–TFSA anionic assemblies connected by hydrogen bonds.     

Ancillary ligand-controlled assembly of three coordination polymers: synthesis,characterization, luminescent,and catalytic properties

Abstract

By changing the ancillary ligands, three new zinc-based coordination polymers (CPs), {[Zn(4,4′-bpy)(H₂O)₄]·(TDC)·(H₂O)}_n (1), [Zn(2,2′-dmbpy)(TDC)]_n (2), and [Zn₂(3,3′-dmbpy)(TDC)₂]_n (3) (H₂TDC =2,5-thiophenedicarboxylic acid, 4,4′-bpy =4,4′-bipyridine, 2,2′-dmbpy =2,2′-dimethyl-4,4′-bipyridine, 3,3′-dmbpy =3,3′-dimethyl-4,4′-bipyridine) have been synthesized under the same reaction conditions (H₂O, pH =7–8, and 140°C) and were structurally characterized. 1 is a linear chain structure and further connected into a 3-D structure through hydrogen bonds. 2 shows a 2-D (4,4) network when the dinuclear [Zn₂(COO)₄N₂] building unit is regarded as a six-connected node. 3 has a twofold-interpenetrating 3-D zinc-organic framework pcu topology. Furthermore, 1–3 show strong photoluminescence at room temperature in the solid state, and the catalytic activities of 1–3 for degradation of methyl orange in a Fenton-like process have been investigated. The results suggest that the ancillary ligands influence the final resulting CPs.     

A series of new oxo-vanadium(IV) complexes with octahedral coordinated vanadium centers

A series of new oxo-vanadium(IV) complexes, [VOCl0.69(OH)0.31 (2,2′-bipy)2]Cl·2H2O (1, 2,2′-bipy?=?2,2′-bipyridine) [(VO)₂Cl₄(4,4'-bipy)₃ (H₂O)₂] (2, 4,4'-bipy?=?4,4'-bipyridine), [VO(ida)(H₂O)]_n (3, H₂ida?=?iminodiacetic acid), and [(VO)₂(oa)₄]_n·4n(H₃O)·n(H₂O) (4, H₂oa?=?oxalic acid), have been synthesized and structurally characterized. 1 contains a [VOCl_0.69(OH)_0.31(2,2′-bipy)₂]⁺ cation, Cl ^– anion and two free H₂O molecules. 2 exhibits a binuclear centrosymmetric moiety built up from two [VOCl₂(4,4'-bipy)(H₂O)] units and one bridging 4,4'-bipy ligand, which provides a rare example of a 4,4'-bipy molecule acting as monodentate ligand. 3 displays a neutral chain [VO(ida)(H₂O)]_n constructed by the linkages of [VO(H₂O)]²⁺ units and ida^2? bridging ligands, while 4 offers the only example of three kinds of oa^2- ligands coexisting within the same anionic chain [(VO)₂(oa)₄^4-]_n. Their spectroscopic properties were investigated, and the magnetic susceptibility of 4 shows antiferromagnetic behavior.     

The assembly of POM-induced inorganic–organic hybrids based on copper ions and mixed ligands

Three inorganic–organic hybrid materials based on Keggin-type polyoxometalates (POMs), [Cu^II₂(phen)₂(4,4′-bipy)(H4,4′-bipy)₂(H₂O)₂][PMo₁₂O₄₀]₂·2H₂O (1), [Cu^II(phen)₂(H4,4′bipy)][PW₁₂O₄₀]·H₂O (2), and [Cu^II₂(phen)₂(4,4′-bipy)(BW₁₂O₄₀)(H₂O)₂](H₂4,4′-bipy)_0.5·3H₂O (3) (phen = 1,10-phenanthroline, 4,4′-bipy = 4,4′-bipyridine), were synthesized using different POMs in the hydrothermal conditions. Compounds 1–3 were characterized by single-crystal X-ray diffraction, IR spectra, elemental analyses, powder X-ray diffraction analyses, and thermogravimetric analyses. Compound 1 presents a two-dimensional (2-D) network containing the Keggin-type [PMo₁₂O₄₀]^3? anion and dinuclear metal–organic units [Cu^II₂(phen)₂(4,4′-bipy)(H4,4′-bipy)₂(H₂O)₂]³⁺. Compound 2 is a 2-D architecture constructed from a [PW₁₂O₄₀]^3? and mononuclear metal–organic units [Cu^II(phen)₂(H4,4′-bipy)]³⁺. In 3, the [BW₁₂O₄₀]^5? anions link [Cu^II₂(phen)₂(4,4′-bipy)] units to form a one-dimensional (1-D) chain [Cu^II₂(phen)₂(4,4′-bipy)(BW₁₂O₄₀)(H₂O)₂]; the 1-D chain connects with protonated 4,4′-bipy ligands and lattice waters, yielding a 2-D layer. Fluorescence spectra, UV–vis spectra, and electrochemical properties of 1–3 have been investigated.     

Structural diversity of a series of urea-based coordination complexes: from water tapes,water-sulfate chains,to supramolecular structures

[Hg₂(L₁)₂I₄] (1), [Cd₂(L₁)₂I₄] (2), {[Cd(L₁)₂(SO₄)(H₂O)]·4H₂O}_n (3), {[Zn₂(L₂)₂(Cl)₄]·0.5H₂O} (4), {[Cu₂(L₂)₂(SO₄)₂(H₂O)₄]·2.5H₂O} (5), and {[Cd(L₂)₂(SO₄)(H₂O)]·3H₂O}_n (6), based on N–(3–picolyl)–N′–(3–pyridyl)urea (L₁) or N–(4–picolyl)–N′–(3–pyridyl)urea (L₂), have been synthesized and characterized by elemental analyses, IR spectra, single-crystal and powder X-ray diffraction, and thermogravimetric analyses. Complexes 1 and 2 are isomorphous and feature similar rectangular metal organic loops, which were further extended into 2-D supramolecular structures through hydrogen bonds. Complex 3 possesses a 2-D sql sheet, and the channels between the neighboring sheets are filled with lattice water molecules, which formed a 1-D water tape. Complex 4 also exhibits a rectangular metal organic loop and a 3-D supramolecular structure with the help of hydrogen bonding interactions. Complex 5 also possesses a metal organic loop, and the water molecules interacted with sulfates, constructing a 1-D water–sulfate tube. Complex 6 features a 1-D loop polymeric chain. Moreover, the solid state luminescences of 1–4 and 6 have been investigated.     

Syntheses,structures, and properties of four coordination compounds constructed from asymmetric semi-rigid V-shaped multicarboxylate ligand

Four new compounds, [Mn(HL)(phen)₂(H₂O)] (1), [Ni(HL)(phen)₂(H₂O)] (2), [Zn(HL)(4,4′-bipy)_1.5(H₂O)] _n ?·?2nH₂O (3) and [Zn₂(HL)₂(H₂O)₆] (4), have been synthesized from an asymmetric semi-rigid V-shaped multicarboxylate 4-(4-carboxy-phenoxy)-phthalic acid (H₃L) with 1,10-phenanthroline (phen), or 4,4′-bipyridine (4,4′-bipy) as auxiliary ligands. Single-crystal X-ray diffraction analysis reveals that 1, 2 and 4 have 0-D structures with 3-D supramolecular frameworks formed by intermolecular hydrogen bonds. Compound 3 shows a 1-D infinite ribbon bridged by 4,4′-bipy, which further forms a 3-D supramolecular architecture by π–π stacking interactions and hydrogen bonds. Thermal stabilities of 1–4 and luminescence properties of 3 and 4 have also been investigated.     

The construction of two lanthanide coordination polymers based on 5-hydroxyisophthalate and bipyridine

Two lanthanide coordination polymers, [Tm₂·(5-IPA)₄·(2,2′-Hbipy)₂]·3H₂O (1, 5-H₂IPA?=?5-hydroxyisophthalic acid, 2,2′-bipy?=?2,2′-bipyridine) and [Er·(5-HIPA)₃·(4,4′-bipy)₃·(H₂O)₂]·3H₂O (2, 4,4′-bipy?=?4,4′-bipyridine), have formed by hydrothermal synthesis. Complex 1 exhibits a 2-D coordination network containing parallelepiped-shaped voids occupied by guest 2′2-bipy molecules. Complex 2 possesses a 1-D linear chain structure. The 1-D chains are linked by 4,4′-bipy molecules to form a 3-D supramolecular framework. IR spectroscopy, elemental analysis, and thermogravimetric analysis were also investigated.     

New nano-particle La(III) supramolecular compound as a precursor for preparation of lanthanum oxybromide-, hydroxide-, and oxide-nanostructures

Nano-particles of a new La(III) supramolecular compound [La(4,4′-bipy)(H₂O)₂(NO₃)_3.75Br_0.25] · (4,4′-Hbipy) (1), have been synthesized from reaction of 4,4′-bipy with La(NO₃)₃ and NaBr by the sonochemical method. For the first time LaOBr, La(OH)₃ and La₂O₃ nano-structures were prepared from [La(4,4′-bipy)(H₂O)₂(NO₃)_3.75Br_0.25] · (4,4′-Hbipy) (1) by calcination at 400, 500, and 700°C, respectively. The structure of 1 was determined by X-ray crystallography and the nano-structures were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Thermal stabilities of nano and crystal samples of 1 were studied and compared with each other.     

Syntheses,crystal structures,and optical properties of a series of transition metal coordination polymers with chelidamic acid and 4,4′-bipyridine

A series of transition metal (Zn, Cu, Mn) complexes with chelidamic acid (2,6-dicarboxy-4-hydroxypyridine, H₃CAM) and 4,4′-bipyridine (bipy), [Zn₂(bipy)Cl₂] _n (1), {[Zn₂(HCAM)(H₂CAM)₂]?·?(bipy)?·?3.5H₂O} _n (2), [Mn₃(HCAM)₃(H₂O)₇]?·?(bipy)?·?3H₂O (3), [Mn₂(HCAM)₂(bipy)?·?(H₂O)₂]?·?4H₂O (4), [Cu₂(HCAM)₂(bipy)?·?(H₂O)₂]?·?4H₂O (5), and Cu₂(HCAM)₂(bipy)?·?(H₂O)₂ (6), have been synthesized by hydrothermal or solution methods and characterized by single-crystal X-ray diffraction. The structural analyses reveal that 1 exhibits a zigzag chain of Zn(II), Cl^?, and 4,4′-bipyridine. In 2, a 1-D polymeric [Zn₂(HCAM)(H₂CAM)₂] _n chain and a discrete 4,4′-bipyridine assemble into a 2-D supramolecular network via H-bonds. Complex 3 consists of asymmetric units of Mn₃(HCAM)₃(H₂O)₇ that are linked by hydrogen bonds to form a 2-D H-bonded network. Complexes 4–6 are isomorphous and possess discrete structures. The photoluminescent properties of 1–6 at room temperature were studied.     

Syntheses and crystal structures of phthalato-, succinato-, maleato-, acetylenedicarboxylato-bridged [bis(2-pyridylcarbonyl)amide]copper(II) complexes

Self-assemblies of the 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and Cu(OH)₂ in the presence of dicarboxylate ligands yielded four new complexes, [Cu₄(bpca)₄(L1)₂(H₂O)₂]·5H₂O (1), [Cu₂(bpca)₂(L2)(H₂O)₂]·2H₂O (2), [Cu₂(bpca)₂(L3)(H₂O)₂]·H₂O (3), and [Cu₂(bpca)₂(L4)(H₂O)₂]·3H₂O (4) (bpca = bis(2-pyridylcarbonyl)amide anion, H₂L1 = phthalic acid, H₂L2 = succinic acid, H₂L3 = maleic acid, H₂L4 = acetylenedicarboxylic acid). Their structures were determined by single-crystal X-ray diffraction analyzes and further characterized by IR spectra and thermogravimetric analyzes. The five-coordinate Cu ions in 1 are bridged by phthalate to form 1-D chains, which are assembled into 3-D frameworks by extensive hydrogen bonds. Compounds 2–4 possess similar structures, built up of [Cu₂(bpca)₂(L)(H₂O)₂] (L = L2 for 2, L3 for 3, L4 for 4) and lattice molecules. The 3-D frameworks of 2–4 are completed by hydrogen bond interactions.     

Five metal imidazole dicarboxylate-based compounds comprising M3(MIDC)2 entities (M = Zn2+, Co2+, Mn2+): syntheses,structures and properties

Five metal imidazole dicarboxylate-based compounds, {[Zn₃(MIDC)₂(4,4′-bipy)₃](4,4′-bipy)·8H₂O}_n (1), {[Co₃(MIDC)₂(4,4′-bipy)₃](4,4′-bipy)·6H₂O}_n (2), {[Co₃(MIDC)₂(py)₂(H₂O)₂]}_n (3), {[Mn₆(MIDC)₄(py)₅(H₂O)₄]}_n (4), and {[Mn₃(MIDC)₂(Phen)₃(H₂O)₂]}_n (5) (H₃MIDC = 2-methyl-1H-imidazole-4,5-dicarboxylic acid; 4,4′-bipy = 4,4′-bipyridine; py = pyridine; Phen = 1,10-phenanthroline), have been synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. We control the coordination modes of H₃MIDC via hydrazine and obtained a series of coordination compounds containing honeycomb-like [M₃(MIDC)₂]_n layers. We also investigated the effects of different neutral terminal or bridging ligands on [M₃(MIDC)₂]_n layers. Coplanar [M₃(MIDC)₂]_n layers and 4,4-bipy were used to construct 3-D frameworks of 1 and 2. Puckered [M₃(MIDC)₂]_n layers were found in 3–5; 4 is the first [M₃(L)₂]_n layer structure with two crests and troughs during each period (L = imidazole-4,5-dicarboxylic acid or its analog). Compound 5 is the first puckered [M₃(L)₂]_n layer structure decorated by chelating neutral ligands. Compound 1 exhibits weak blue photoluminescence in the solid state at room temperature. Variable-temperature magnetic susceptibility measurements of 2–5 indicate strong antiferromagnetic interactions.     

Syntheses,crystal structures,and magnetic properties of 1-D coordination polymers

Three coordination polymers of Robson-type macrocycles, {[Cu₄L¹(4,4′-bipy)₂]·4ClO₄·H₂O}_∞ (1), {[Cu₄L²(4,4′-bipy)₄]·2CH₃CN·4ClO₄·2H₂O}_∞ (2), and {[Zn₂L²(4,4′-bipy)₂]·(ClO₄)₂}_∞ (3) (where H₂L¹ and H₂L² are the [2?+?2] condensation products of 1,3-diaminopropane with 2,6-diformyl-4-methylphenol and 2,6-diformyl-4-fluorophenol, respectively), have been synthesized and characterized. Magnetic susceptibility was measured for 1 and 2 from 2 to 300?K. The optimized magnetic data were J?=?–368.5?cm^?1, J′?=?40.5?cm^?1 with R?=?1.69?×?10^?6 for 1 and J?=?–291.22?cm^?1, J′?=?83.74?cm^?1, ρ = 0.00168 with R?=?1.8?×?10^?11 for 2, respectively. The data reveal strong antiferromagnetic interactions between two Cu(II) ions in the macrocyclic unit and ferromagnetic interaction between the Cu(II) ions in two adjacent macrocyclic units for 1 and 2.