A lead(II)-orotate coordination polymer with a new coordination mode: Synthesis,structure and luminescent property

A lead(II) orotate complex [Pb(HOr)(H₂O)]_n (1), (H₃Or = orotic acid) was synthesized under hydrothermal condition and characterized by X-ray diffraction, IR, solid-state photoluminescence and thermogravimetric analysis. Lead atom in 1 is in a holodirected eight-coordinated polyhedron and the orotate ligand exhibits a new and unique hexametallic coordination mode. The lead complex shows a 6,6-connected (4⁸, 6⁶, 8)(4¹³, 6²) topology. The complex exhibits photoluminescence at 546 nm (λ_ex = 350 nm).     

Self-assembly of an organo-palladium molecular basket that encapsulates cobalticarborane anion in water

Two [M₃L₃]^6 +-type organo-palladium(II) macrocyclic host molecules, {[(phen)Pd]₃(4,7-phen)₃}(NO₃)₆, 1·6NO₃⁻; {[(dtod-phen)Pd]₃(4,7-phen)₃}(NO₃)₆, 2·6NO₃⁻, (where M = (4,7-phen)Pd, (dtod-phen)Pd; 4,7-phen = 4,7-phenanthroline (L), phen = 1,10-phenanthroline, dtod-phen = 5,6-di(1′,4′,7′,10′-tetraoxododecanoxy)-1,10-phenanthroline), have been synthesized by metal-directed self-assembly in aqueous solution. These basket-shaped hosts bearing syn, syn, syn orientations and their anion complexes, have been fully characterized by ¹H NMR, cold-spray ionization mass spectrometry (CSI-MS) and in the case of basket-shaped host 1*PF₆⁻ by X-ray single-crystal diffraction analysis. On the basis of anion binding structure within the cavity of 1, the molecule basket 2 possessing a hydrophobic inner cavity expanded with hydrophilic polyethyleneglycol chains was successfully designed for encapsulating one giant anion [(C₂B₉H₁₁)₂Co]⁻ in water and the host–guest interaction was studied by ¹H NMR titration and CSI-MS.     

Photoluminescent metal–organic coordination polymer incorporating one-dimensional silver chains

Solution phase reaction of AgNO₃ with a mixture of benzene-1,3,5-tricarboxylic acid (H₃BTC) and heterocyclic 2-aminopyrimidine (APYM) under the ammoniacal conditions gives rise to a novel metal–organic coordination polymer Ag₃(BTC)(APYM)₂ (1). The structure of 1 possesses a unique three-dimensional (3D) framework with one-dimensional channels surrounded by carboxylato-supported Ag–Ag dimers, Ag–Ag chains, fully deprotonated [BTC]^3? and APYM ligands. Moreover, 1 exhibits strong blue photoluminescence maximized at 464 nm at room temperature (λ_ex = 383 nm) and upon cooling to 77 K, the emission spectrum seems narrowly red-shifted.     

Highly efficient near-infrared (NIR) luminescent tris-β-diketonate Yb3 + complex in solution and in PMMA

In the series of binary tris-β-diketonate complexes [Ln(L)₃(Phen)] (HL = (Z)-3-methyl-1-phenyl-4-(2,2,2-trifluoro-1-hydroxyethylidene)-1H-pyrazol-5(4H)-one; Phen = 1,10-phenanthroline; Ln = La, 1; Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5), the relatively lower ligands-based ³ππ^⁎ energy level (18,727 cm^− 1) results in the highly efficient NIR luminescence (Ф_Yb^Yb = 1.37% and Ф_Yb^L = 1.06%) of Yb^3 +-based 3 in solution and the higher NIR quantum yield (Ф_Yb^Yb = 1.77% and Ф_Yb^L = 1.31%) in PMMA (Poly(methyl methacrylate) besides the improved physical properties.     

Preparation and chemical properties of π-conjugated poly(1,10-phenanthroline-3,8-diyl)s with crown ether subunits

π-Conjugated polymers consisting of 1,10-phenanthroline units and crown ether subunits (Poly-1, Poly-2, and Poly-3) were prepared by dehalogenation polycondensation of the corresponding dibromo monomers using a zero-valent nickel complex as a condensing agent. They were characterized by elemental analysis, ¹H NMR and UV–Vis spectroscopies, and cyclic voltammetry (CV). They were partly soluble in CHCl₃, and the number average molecular weight of the soluble part of Poly-2, which had 15-crown-5 subunits, was estimated to be 5300. The polymers exhibited UV–Vis peaks at approximately λ_max = 360 nm, which was reasonable. Complexation with [Ru(bpy)₂]²⁺ and alkaline metal ions made the polymer soluble in organic solvents. The complexation of [Ru(bpy)₂]²⁺ to the 1,10-phenanthroline unit proceeded quantitatively, and the [Ru(bpy)₂]²⁺ complexes exhibited CV curves characteristic of [Ru(N-N)₃]²⁺ complexes.     

Photo- and electroluminescence from deep-red- and near-infrared-phosphorescent tris-cyclometalated iridium(III) complexes bearing largely π-extended ligands

Deep-red- and near-infrared-phosphorescent tris-cyclometalated iridium(III) complexes bearing largely π-extended cyclometalated (C^N) ligands were newly synthesized, and their photo- and electroluminescence properties were investigated. When 2-(benzo[b]furan-2-yl)quinoline and 2-(benzo[b]thiophen-2-yl)quinoline were employed as C^N ligands, deep-red photoluminescence was obtained (Ir-1a and Ir-1b; λ_PL in CH₂Cl₂, 647 and 652 nm, respectively). In the case of the isoquinoline analogues of Ir-1a and Ir-1b, emission maxima were further red-shifted, ranging from deep-red to near-infrared regions (Ir-2a and Ir-2b; λ_PL in CH₂Cl₂, 696 and 690 nm, respectively). Especially, Ir-2b showed an excellent photoluminescence quantum yield (Φ_PL = 0.15), and a polymer light-emitting diode doped with Ir-2b exhibited deep-red–near-infrared electroluminescence with a high external quantum efficiency (λ_EL = 694 nm, η_{ext max} = 1.41%).     

Syntheses,crystal structures and luminescence properties of lanthanide coordination polymers involving in situ C–S bond cleavage of (4-pyridylthio)acetic acid

Lanthanide coordination polymers with the formula [Ln₂(C₂O₄)₃(H₂O)₆]_n (1) (Ln = Nd, 1) and [Ln₂(C₂O₄)₃(pythioH)₂(H₂O)₂]_n (Ln = Eu 2; Dy 3; Er 4) pythio = 4-pyridinethiolate) were synthesized by treating Ln^III nitrates with (4-pyridylthio)acetic acid under hydrothermal conditions. Single-crystal X-ray diffraction studies indicate that these lanthanide coordination polymers consist of extended oxalate-bridged two-dimensional layer structure. Interestingly, in situ C–S bond cleavage occurred and (4-pyridylthio)acetic acid was transformed into 4-pyridinethiolate and oxalate. The complexes 2 and 3 display strong fluorescent emission in the solid state at room temperature.     

Formation of three-dimensional supramolecular water architectures containing 1D water chains via dianion templating

A three-dimensional supramolecular water architectures: [Ni(phen)₃](C₁₀H₁₆O₄) · (C₁₀H₁₈O₄)_0.5 · 11H₂O (1) [phen = 1,10-Phenanthroline, C₁₀H₁₆O₄ = sebacic dianion, C₁₀H₁₈O₄ = sebacic acid] has been synthesized and characterized by IR, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffractions. 1D water chains behave as pillars to join these water sheets to make an overall three-dimensional supramolecular architecture by hydrogen-bonding interactions.     

Construction of two-dimensional supramolecular structure containing water tetramer and octamer

The complex [Cd₂(phen)₄(p-phth)(H₂O)₂](p-phth) · 10H₂O (1) has been synthesized by the reaction Cd(NO₃)₂ with phen and p-phth (where phen = 1,10-phenanthroline, p-phth = p-phthalic acid) in a solution of ethanol and distilled water. The crystal structure was characterized by X-ray single-crystal diffraction and infrared spectrum. In 1, a novel 2D supramolecular structure was formed, containing water octamer and tetramer.     

Synthesis,structure, and properties of two novel copper(II) complexes, [Cu(phen)(L)2]·6H2O and [Cu(phen)3]·(ClO4)2

Two novel copper(II) complexes, namely [Cu(phen)(L)₂]·6H₂O (1) and [Cu(phen)₃]·(ClO₄)₂ (2) have been synthesized under mild condition (HL = 5-methyl-1H-pyrazole-3-carboxylic acid, phen = 1,10-phenanthroline). We report the structural evidence of discrete water decamer conformation in the solid state. These units are found to act as supramolecular glue in the aggregation of mononuclear copper(II) complex to give a three-dimensional network through hydrogen-bonding. The preliminary investigation on the thermal behavior and the anion exchange property of the complexes are presented.     

Polycatenated (4, 4) lanthanide(III) coordination networks based on apidate: Synthesis,structure and properties

Three rare earth coordination polymers, {[Ln₂(μ₃-ADI)₂(μ₂-ADI)(H₂O)₄]·H₂O}_n (Ln = Tb, 1; Eu, 2; Er, 3; ADI = adipate), which show the inclined interpenetration of (4, 4) nets and bright luminescence, were isolated from H₂PDC-assisted (H₂PDC = pyridine-2,3-dicarboxylatic acid) hydrothermal reactions of H₂ADI and Ln₂O₃.     

Syntheses and magnetic properties of trinuclear trithiocyanurato-bridged manganese(II) complexes involving bidentate aromatic N-donor heterocycles

Trinuclear manganese(II) complexes of the compositions [Mn₃(phen)₆(ttc)](ClO₄)₃ (1), [Mn₃(dmbpy)₆(ttc)](ClO₄)₃? 2H₂O (2) and [Mn₃(bpy)₆(ttc)](ClO₄)₃? 3H₂O (3), where phen = 1,10-phenanthroline, dmbpy = 4,4′-dimethyl-2,2′-bipyridine, bpy = 2,2′-bipyridine and H₃ttc = trithiocyanuric acid (2,4,6-trimercapto-1,3,5-triazine), were prepared and characterized by elemental analysis, FTIR and Raman spectroscopies, MALDI-TOF mass spectrometry, magnetic and conductivity measurements. The magnetic analysis incorporating simultaneous fitting of the temperature dependence and the field dependence of the magnetization using the isosceles triangle spin Hamiltonian model revealed a weak antiferromagnetic exchange within the trinuclear units.     

Construction of a new 3D Zn(II) coordination polymer with (4,6)-connected topology: Synthesis,structure and luminescence

A new coordination polymer of {[Zn₂(odpa)(IP)]·4H₂O}_n (1) (H₄odpa = 3,3′,4,4′-oxydiphthalic acid and IP = 1-H-imidazo[4,5-f][1,10]-phenanthroline), is reported. The 3D (4,6)-connected {4⁴∙6²∙8⁸∙12}{4⁴∙6²} topology net is formed by IP and odpa ligands in 1. Interestingly, the IP ligand acts as a tridentate mode and extends the resulting 3D feature. The luminescence study indicates that the title compound emits bright red fluorescence.     

Coordination polymers from 1-D to 3-D assembled from disulfonate ligands: Structures and luminescent properties

Four rare earth organodisulfonate coordination polymers, {[Tb₂(phen)₄(nds)₃(H₂O)₂]·4H₂O}_n (1), {[Ln(phen)(nds)(OH)]}_n[Ln = Sm (2), Nd (3)], {[Tb(phen)₂(nds)_0.5(OH)·H₂O]·(nds)_0.5}_n (4), were synthesized under the solvothermal conditions by using ligands 2,6-naphthalenedisulfonate (L = nds) and 1,10-phenanthroline (L′ = phen). Single-crystal X-ray diffraction reveals that compounds 1 and 4 exhibit different 1-D and 2-D crystal structures just owing to the single difference of stoichiometric ratio of the reactants in the synthesis process. Compounds 2 and 3 show 3-D structures with similar Ln coordination mode. Besides, the photoluminescent property in solid state of 1 was investigated in detail.     

Near-infrared (NIR) luminescent homoleptic linear tetranuclear [Ln4((OH)2-Salophen)4] (Ln = Nd or Yb) complexes self-assembled from the dihydroxylated Salophen ligand

Through self-assembly of the (OH)₂-Salophen H₄L (H₄L = N, N′-bis(3-hydroxyl salicylidene)benzene-1,2-diamine) with LnCl₃·6H₂O (Ln = La, Nd, Yb, Er or Gd), series of [Ln₄((OH)₂-Salophen)₄]-arrayed complexes [Ln₄(H₂L)₂(L)₂(EtOH)₂] (Ln = La, 1; Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5) were obtained, respectively. The result of their photophysical properties shows that the strong and characteristic NIR luminescence for complexes 2–3 with emissive lifetimes in microsecond ranges is observed, and the sensitization arises from the excited state (¹LC) of the (OH)₂-Salophen ligand despite the luminescent quenching with OH-oscillators around the Ln^3 + ions.     

Fluorescent selectivity for small molecules of two coordination polymers based on a tetracarboxylate ligand

Two coordination polymers [Cd(tptc)_0.5(4,4′–bibp)]_n (1) and {[Zn₃(Htptc)₂(phen)₂]·1.5H₂O}_n (2) (H₄tptc = terphenyl-3,3″,5,5″-tetracarboxylic acid, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl, and phen = 1,10-phenanthroline) were synthesized under solvothermal conditions. Complex 1 displays a 3D structure with a Schläfli symbol of {4⁴.6²}{4⁸.6²⁰}. Complex 2 possesses a 2D layer network, incorporating [Zn₃(COO)₆] second building units (SBUs), which is packed into a 3D supramolecular architecture by π ⋯ π interactions. Both of them exhibit strong luminescence characteristics. It is worth to note that complexes 1 and 2 show potential application to detect small organic molecules.     

Hetero-trinuclear near-infrared (NIR) luminescent ZnLn2 (Ln = Nd,Yb or Er) complexes based on monomer ZnL Schiff-base precursor and o-vanillin

With the monomer [Zn(L¹)(H₂O)] (1) complex in situ formed by the deprotonated hexadentate Salen-type Schiff-base ligand H₂L¹ (H₂L¹ = N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) and Zn(NO₃)₂ as the precursor, series of the hetero-trinuclear ZnLn₂ complexes [ZnLn₂(L¹)₂(L²)(NO₃)₂Cl] (Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5) were obtained from the further reaction with LnCl₃ (Ln = Nd, Yb Er or Gd) and the second o-vanillin (HL²) ligand, respectively. The photophysical properties of complexes 2–4 showed that the characteristic near-infrared (NIR) luminescence of Ln^3 + ions with two emission centers and emissive lifetimes in microsecond ranges, was sensitized from the excited state (both ¹LC and ³LC) of mixed H₂L¹–HL² ligands.     

A series of lanthanide (III) coordination polymers derived via in situ hydrothermal decarboxylation of quinoline-2,3-dicarboxylic acid

A series of one-dimensional coordination polymers assembled from LnNO₃ · 6H₂O (Ln = Sm(1), Eu(2), Tb(3), La(4), Ce(5), Pr(6), Nd(7), Dy(8)), quinoline-2,3-dicarboxylic acid (2,3-H₂qldc) and 1,10-phenanthroline (phen) formulated as [Ln(2,3-qldc)(3-qlc)(phen)]_n (3-Hqlc = quinoline-3-carboxylic acid) were obtained under hydrothermal conditions. It is remarkable that in situ hydrothermal decarboxylation was observed during preparing these polymers. Complexes 1–8 were characterized by elemental analyses, IR spectroscopy and single crystal X-ray diffraction analyses. The thermal stabilities and photoluminescence properties of these complexes have been investigated.     

Syntheses and characterizations of two-dimensional lanthanide coordination polymers based on anthraquinone-1,4,5,8-tetracarboxylic acid

A series of isostructural two-dimensional lanthanide complexes with the formula [Ln(Haqtc)(H₂O)₄·xH₂O]_n (Ln = Nd, 1; Sm, 2; Eu, 3; Tb, 4; Dy, 5; Er, 6.) were synthesized by treating H₄aqtc (H₄aqtc = anthraquinone-1,4,5,8-tetracarboxylic acid) with lanthanide(III) salts under hydrothermal conditions. 3-D structures are formed by inter-layer hydrogen bonds. Magnetic susceptibility measurements of complexes 4 and 5 in temperature range 2–300 K were performed, which showed dominant weak ferromagnetic interactions in 4 and slow magnetization relaxation in 5.     

A tetranuclear pyrophosphate-bridged Cu(II) complex with 4,4′-bipyridine and 1,10-phenanthroline: Synthesis,structural, and magnetic properties

A new tetranuclear pyrophosphate-bridged Cu(II) complex with 4,4′-bipyridine and 1,10-phenanthroline [Cu₄(phen)₄(bpy)₂(P₂O₇)₂]·10H₂O (1) has been hydrothermal synthesized and characterized by single-crystal X-ray analysis, element analysis, IR spectroscopy, TG analysis, and UV–vis spectra. Variable-temperature magnetic susceptibility measurements show the occurrence of antiferromagnetic interactions between the neighbor Cu(II) centers in 1. The analysis of the magnetic data in the whole temperature range allows the determination of the value of the intramolecular magnetic coupling (J = − 13.16 cm^− 1).