First hexanuclear manganese(II) μ6-Cl centered carboxylate anion: Synthesis,structure and magnetic properties

Reaction of manganese(II) polymer [Mn₅Cl(OH)(Piv)₈(MeCN)(HPiv)(H₂O)]_n (1, HPiv is pivalic acid) and 2-benzoylpyridine (L) in MeCN produces the ionic complex [Mn₃(Piv)₅L₂(MeCN)]⁺[Mn₆Cl(Piv)₁₂]⁻ · MeCN (3) containing the unusual hexanuclear {Mn₆(μ₆-Cl)} anion. An analogous anion was also observed in the complex [Mn₆Cl(Piv)₁₂]⁻(NEt₄)⁺ · 5MeCN (4) prepared by the reaction of the polymer [Mn(Piv)₂(EtOH)]_n (2) with NEt₄Cl in MeCN. Complexes 3 and 4 were characterized by the X-ray diffraction and magnetic susceptibility.     

A heterometallic approach for enhancing the net robustness of metal-organic framework

With the help of a heterometallic approach, an unstable channel-type framework {[Cu₄Cl(CPT)₄]·(NO₃)₃·5DMF}_n (1, HCPT = 4-(4H-1,2,4-triazol-4-yl)benzoic acid, DMF = N,N-Dimethylformamide) is structurally modified into a robust channel-type framework {[InCu(OH)(CPT)₂]·(NO₃)₂·(DMF)₄}_n (2) via embedding independent indium-based units into the Cu(II)-organic framework, in which the 1D In(III)-chains and 1D Cu(II)-chains coexist. Although both MOFs have similar framework structures, the activated heterometallic MOF 2 exhibits a BET surface area of 1032 m²/g, which is extraordinary high compared with that of the activated 1. In addition, the gas sorption property of MOF 2 around room temperature has also been investigated.     

PNBE-supported metallopolymer-type hybrid materials through grafting of Ln3-benzimidazole-arrayed (Ln = Nd,Yb or Er) complex monomers with efficient NIR luminescence

Through the ring-opening metathesis polymerization (ROMP) of norbornene (NBE) with each of the obtained allyl-containing complex monomers {[Ln₃(L)₄Cl₄(MeOH)₂]·Cl} (Ln = La, 1; Nd, 2; Yb, 3; Er, 4 or Gd, 5; HL = 4-allyl-2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol), a series of metallopolymers Poly({[Ln₃(L)₄Cl₄(MeOH)₂]·Cl}-co-NBE) were obtained, respectively. Especially for Poly(NBE-co-2) and Poly(NBE-co-3), covalently-bonded grafting endows significantly improved physical properties including efficient NIR luminescence (Φ_Nd^L = 0.58% and Φ_Yb^L = 0.88%) in solid state.     

A luminescent europium metal–organic framework with free phenanthroline sites for highly selective and sensitive sensing of Cu2 + in aqueous solution

A luminescent europium metal–organic framework [Eu(HL)(L)(H₂O)₂]·2H₂O (1) (H₂L = (2,3-f)-pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid) with uncoordinated phenanthroline nitrogen sites was hydrothermally synthesized. It exhibits highly sensitive and selective sensing of Cu^2 + in aqueous solution. To the best of our knowledge, complex 1 is the first luminescent Eu-MOF with uncoordinated phenanthroline nitrogen sites for selective sensing of Cu^2 + in aqueous solution. The probable sensing mechanism was discussed in detail.     

Three cobalt (II) complexes with triethylenetetraaminehexaacetic acid: From binuclear complex to 3d-4f coordination polymers

The cobalt(II)–lanthanide(III) heteronuclear complexes [Ln(H₂O)₄Co₂(TTHA)(SCN)₂]·H₃O⁺ (H₆TTHA = triethylenetetraaminehexaacetic acid, Ln = La(2), Ce(3)) have been synthesized based on a binuclear building block of [Co₂(H₂TTHA)(H₂O)₂] in [Co₂(H₂TTHA)(H₂O)₂]·4H₂O (1). Single-crystal structures show that complex 1 is a binuclear complex, containing the [Co₂(H₂TTHA)(H₂O)₂] unit as a useful building block. Adding the La^3 + and Ce^3 + ions to this synthesis system, two new 3d-4f mixed complexes 2 and 3 were obtained. Complexes 2 and 3 show 3D framework, comprising an infinite 1D (one-dimensional) chain based on heterometallic Ln₂Co₂ (Ln = La(2), Ce(3)). Further investigations such as IR spectra, UV–vis spectra, TGA, XRD and magnetic properties were studied.     

Two organic–inorganic hybrid materials based on the penta-nuclear {MMn4} (M = W and Mo) heterometallic clusters and Schiff-base ligands

Two organic–inorganic hybrid compounds with the formula {[Mn^III(Salen)(H₂O)]₄MoO₄}·Cl₂·16H₂O (1) and {[Mn^III(Salen)(H₂O)]₄WO₄}·(CH₃COO)₂·11H₂O (2) (Salen = Di-[2-hydroxyl-3-methoxyl-benzaldehyde] ethylenediamine) have been synthesized and structurally characterized by IR, UV–vis spectroscopy, TG analysis and single crystal X-ray diffraction. Structural analysis revealed that compounds 1 and 2 consist of a [MoO₄]^2 − or [WO₄]^2 − building unit and four {[Mn^III(Salen)(H₂O)]⁺ metal–organic moieties, respectively. In the crystal structure, the [MoO₄]^2 − or [WO₄]^2 − tetrahedra coordinated with four Mn^III ions, resulting in the penta-nuclear heterometallic tetrahedra cluster compounds, which were rarely observed in the Mn-Salen system. Magnetic study revealed that there was antiferromagnetic coupling in the two compounds.     

Synthesis,characterization and crystal structure of one Mn(II) complex with 4,4′-bisimidazolylbiphenyl and 4,4′-sulfonyldibenzoic acid

One new title compound [Mn₃(BIBP)(sdb)(NO₂⁻)₂(H₂O)₂]_n·2DMF (1) (BIBP = 4,4′-bisimidazolylbiphenyl, sdb = 4,4′-sulfonyldibenzoic acid) has been synthesized under hydrothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction. Magnetic susceptibility measurements indicate that compound 1 exhibits antiferromagnetic coupling interaction.     

Three novel bismuth-based coordination polymers: Synthesis,structure and luminescent properties

Three novel bismuth-based coordination polymers, [(CH₃)₂NH₂][Bi(pdc)(bdc)]·2DMF, [(CH₃)₂NH₂][Bi(tdc)₂]·1.5DMF and [Bi(bpdc)₂H₂O]·xGuest (compounds 1–3) (H₂pdc = 3,5-pyridinedicarboxylic acid, H₂bdc = 1,4-benzenedicarboxylic acid, H₂tdc = 2,5-thiophenedicarboxylic acid, H₂bpdc = 4,4′-biphenyldicarboxylic acid), have been successfully synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction. Compounds 1 and 2, which are constructed by 9-coordinated or 8-coordinated Bi^3 +, feature three-dimensional structures with hms and dia topology, respectively. However, 5-coordinated Bi^3 + based compound 3 is a two-dimensional layered structure. Compound 1 can tune emissive performance by doping different lanthanide ions Tb^3 +, Eu^3 + and Dy^3 +. Furthermore, detection of nitro explosives is investigated. All of the compounds are characterized by elemental analysis, IR spectrum and thermogravimetric analysis.     

Two highly connected frameworks and one polythreading architecture based on multidentate N-donor ligands: Syntheses,structures, characterizations and photoluminescent properties

Three coordination polymers based on multidentate N-donor ligands and polycarboxylate anions, namely, [Co₃(4,4′-tmbpt)₄(btc)₂]·9.5H₂O (1), [Ag₄(4,4′-tmbpt)(btec)(H₂O)₂]·H₂O (2) and [Zn(4,4′-tmbpt)(btec)_0.5(H₂O)]·0.5H₂O (3) (4,4′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole, H₃btc = 1,3,5-benzenetricarboxylic acid, and H₄btec = 1,2,4,5-benzenetetracarboxylic acid) have been prepared under hydrothermal condition. Compound 1 displays a 3D (3,6,8)-connected framework with (4·6²)(4⁴·6¹⁰·8)(4¹⁴·6¹²·8²) topology. Compound 2 is a 3D (4,5,8)-connected framework with (4³·6²·8)(4³·6⁵·8²)(4⁸·6²)(4¹⁰·6¹⁰·8⁸) topology. Compound 3 exhibits a 2D → 3D polythreading architecture. The photoluminescent spectra indicate that at room temperature, compounds 2 and 3 emit green and blue luminescence, respectively.     

A palladium(II) complex of 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine: Lattice control through an interplay of stacking and hydrogen bonding effects

The complex [Pd(1)Cl]Cl where 1 =  4′-(4-pyridyl)-2,2′:6′,2″-terpyridine is reported. The single crystal structure of [Pd(1)Cl]Cl · 3H₂O · DMF features rows of columns of [Pd(1)Cl]⁺ cations which are supported by Pd⋯Pd interactions (3.367(1) and 3.440(1) Å) and separated by hydrogen-bonded 4.8² nets of water molecules and Cl⁻ ions.     

Constructing two new crystalline metal–organic frameworks based on a mixed-donor ligand

The self-assembly of a prominent ligand, 5-(4-(1H-tetrazolyl)phen)isophthalic acid (H₃TZPI), with Zn^2 +/Cu^2 + centres generates two new MOFs, [Zn₂(TZPI)(μ₃-OH)(H₂O)₂]·2H₂O (JUC-161) and [Cu(HTZPI)(μ₂-H₂O)_0.5(H₂O)_1.5]·5(H₂O) (JUC-162). JUC-161 exhibits fascinating three-dimensional structures containing rectangular channels with dimensions of 6.5 × 3.0 Å², and JUC-162 displays 3D supramolecular structures with 12.5 × 14.6 Å² hexagonal channels. The observed structural diversity in these frameworks is due to the two distinct coordinating moieties of the H₃TZPI ligand. The photoluminescence of JUC-161 and the magnetic properties of JUC-162 are also measured at room temperature. Photoluminescence investigations reveal that JUC-161 displays a strong main emission spectrum peak at 388 nm. JUC-162 is found to exhibit an antiferromagnetic interaction between Cu^2 + ions.     

Three d10 coordination polymers based on rigid ligands with flexible functional groups: Syntheses,structures and luminescence

Three coordination polymers, namely, {[Zn(L)(BPY)]·DMF·H₂O}_n (1), {[Zn(L)(TPY)]·0.5H₂BDC·H₂O}_n (2), {[Cd(L)(H₂O)₂]·DMF}_n (3), have been synthesized based on a rigid linear carboxylate ligand (H₂L = 2′,5′-dimethoxy-[1,1′:4′,1″-terphenyl]-4,4″-dicarboxylic acid) and different lengths of pyridine ligands (TPY = 4,3′:5′,4″-terpyridine; BPY = 4,4′-bipyridine). These complexes have been characterized by single crystal X-ray diffraction, infrared spectroscopy, thermogravimetry, elemental analysis, and powder X-ray diffraction measurements. Complex 1 is a 6-connected 3-fold interpenetrating pcu net with point symbol {4¹² ∙ 6³}, 2 and 3 can be simplified as 4-connected sql nets with point symbol {4⁴ ∙ 6²}. In addition, their photoluminescent properties are also investigated in detail.     

A MnII5 tetragonal pyramid stabilized by p-tert-butylcalix[8]arene: Synthesis,structure and magnetic property

A compound, [Mn₅(H₄C8A)(OH)₂(C₃H₆NO₂)(DMF)₅(CH₃O)_1.5(HCO₂) (C₂H₃O₂)_0.5]·2DMF·CH₃OH (1) (H₈C8A = p-tert-butylcalix[8]arene, DMF = N,N′-dimethylformamide), was synthesized by the solvothermal method in the mixed CH₃OH/DMF (1:1) solvent. Compound 1 is featured with a tetragonal pyramid-like Mn^II₅ cluster encircled within a calix[8]arene molecule with a ‘pleated loop’ conformation. Magnetic study indicates that the Mn^II centers exhibit antiferromagnetic interactions.     

Spectroscopic studies on bis(1-amidino-O-alkylurea) copper(II) sulfate complexes where alkyl = methyl,ethyl, n-propyl or n-butyl: EPR evidence for binuclear complexes

Four new Cu(II) Complexes viz. [Cu(II)(1-amidino-O-methylurea)₂]SO₄·2H₂O (1), [Cu(II)(1-amidino-O-ethylurea)₂](SO₄)₂·2H₂O (2), [Cu(II)(1-amidino-O-n-propylurea)₂] SO₄·2H₂O (3), [Cu(II)(1-amidino-O-n-butylurea)₂]₂(SO₄)₂·2H₂O (4) have been synthesized and characterized. EPR spectrum of complex 4 at RT consisted of fine-structure transitions (ΔMs = ±1) with zero-field splitting (ZFS) of 0.0485 cm^?1 and a half-field signal (ΔMs = ±2) at ca. 1600 G, revealed formation of binuclear complex (S = 1). Whereas EPR spectrum of complex 2 in DMSO showed a mixture of mononuclear and binuclear complex in the ratio 0.75:1.0 with ZFS of 0.0385 cm^?1. From the temperature dependence of the EPR signal intensity, the isotropic exchange-interaction constant J was evaluated.     

A novel 3D Zn(II) coordination polymer for highly luminescent sensing of nitro compounds

A novel 3D coordination polymer [Zn_2.5(L)(trz)₂(H₂O)₂]·2H₂O (1) (H₃L = 5-(4-carboxybenzyloxy)isophthalic acid, trz = 1,2,4-triazole) has been synthesized hydrothermally. Compound 1 displays a 3D (3,8)-connected net with (5³)₂(5⁸·6⁴·7⁸·8⁴·9⁴) topology. The luminescent property of 1 dispersed in different solvents as well as nitro compounds have been investigated systematically, demonstrating high detection sensitivity via a fluorescence quenching mechanism.     

Syntheses,structural characterization and electrochemical properties of two rare-earth–isonicotinic-acid containing silicomolybdates

Two rare-earth–isonicotinic-acid containing silicomolybdates [NH₄]₆[RE(INA)₂(HINA)(H₂O)₃]₂[α-SiMo₁₂O₄₀]₂·6H₂O [RE = Nd^III (1), Er^III (2); HINA = isonicotinic acid] have been synthesized in the conventional aqueous solution and characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic P–1 space group and consist of two typical Keggin [α-SiMo₁₂O₄₀]^4 − polyanions, one isolated rare-earth-isonicotinic-acid [RE(INA)₂(HINA)(H₂O)₃]₂^2 + dimeric complex cation, six NH₄⁺ ions and six lattice water molecules. Interestingly, two rare-earth ions are linked by four INA⁻ ligands in the [Ln(INA)₂(HINA)(H₂O)₃]₂^2 + complex cation, which is very rare in polyoxometalate chemistry. The UV spectral measurements of 1 indicate that 1 is stable in aqueous solution in the pH range of 4.49–9.39. Furthermore, the electrochemical and electrocatalytic properties of 1 have been measured by cyclic voltammetry in 0.5 mol·L^− 1 Na₂SO₄ + H₂SO₄ aqueous solution at the scan rate of 100 mV·s^− 1.     

One 2D anionic coordination polymer with {[Co(H2O)6]}2 + cationic guest for fast and selective adsorption of cationic dyes

One new anionic Coordination Polymer, namely [Co(H₂O)₆]^2 +·[Co₃(bptc)₂(H₂O)₁₀]^2 −·3H₂O (1), where H₄bptc = 3,3′,5,5′-biphenyltetracarboxylate, has been synthesized hydrothermally and characterized. In compound 1, bptc^4 − as tridentate ligands connect the Co^2 + cations to form a 2D layer with 1D pseudo channels encapsulation of [Co(H₂O)₆]^2 + guest. In addition, their adsorption activities for organic dyes were investigated in aqueous solution. The results suggested that the anionic complex 1 show rapid and selective adsorption of cationic dyes for Neutral red, Methylene blue.     

An unprecedented ten-connected 3D metal–organic framework based on hexanuclear cobalt(II) cluster building blocks

A 3D metal–organic framework (MOF), [Co₃(μ₃-OH)(μ₂-H₂O)(BPT)(HBPT)(DMF)₂]·(DMF)(H₂O) (1) (DMF = N, N′-dimethylformamide) has been synthesized by self-assembly of cobalt(II) oxide and biphenyl-3, 4′, 5-tricarboxylate (H₃BPT) under solvothermal reaction. Compound 1 displays unique (2,3,10)-connected trinodal connected topology. Besides, 1 represents a rare example of MOF possessing free carboxylic acids. In addition, the magnetic property of the compound is investigated.     

Synthesis,crystal structure and photoluminescent properties of a 3D Zn(II) coordination polymer

A new 3D coordination polymer [NH₂(CH₃)₂]₂[Zn₇L₄(DMF)₂(H₂O)₃]·19H₂O (1) (L = 2,3′,5,5′-biphenyl tetracarboxylic acid) has been solvothermally synthesized and structurally characterized by IR, elemental analysis and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicate that 1 exhibits 3D framework with a one-dimensional (1D) channel. The luminescence properties have been studied, and the results showed that 1 displays strong fluorescent emissions both in the solid state and in methanol suspension at room temperature. More interesting, the addition of Fe^3 + causes the fluorescence intensity of 1 to be weakened, which implies that it may be used as luminescent probes of Fe^3 +.     

Syntheses,crystal structures,and magnetic studies of two cobalt(II) coordination polymers based on concurrent ligand extension

An ether bridged tetracarboxylic acid ligand, 5-(3′,4′-Dicarboxylphenoxy)-isophthalic acid (H₄L) was used to construct two Co(II) coordination polymers in presence of different nitrogen donor ligands such as 4,4′-bipyridine (4,4′-bpy) and 4,4′-bis(pyrid-4-yl)biphenyl (bpbp). The products formed under hydrothermal conditions are formulated as [Co₂L(4,4′-bpy)₂(H₂O)₃]_n (1) and {[Co(bpbp)₂(H₂L)]·H₂O}_n (2). The compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, and powder X-ray diffraction (PXRD) measurement. Compound 1 shows an intriguing (3,4,5)-connected 3D framework with a point symbol of (4² · 6² · 8²)(4² · 6⁵ · 8³)(6² · 8). Compound 2 is an unusual 3D supramolecular framework generated by the one-dimensional [Co(bpbp)(H₂L)]_n polymer chain. The magnetic properties of compounds 1 and 2 were examined, indicating antiferromagnetic interactions between the cobalt(II) ions in the temperature range of 2–300 K.