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A series of lanthanide complexes with mixed polycarboxylate ligands, [Ln2(op)2(ox)(H2O)4]n·nH2O (Ln = Ce, Pr, Nd, Sm, Eu and Gd for 1–6, respectively), [KLn(pma)1/2(ox)(H2O)]n(Ln = Tb (7) and Dy (8)), [KLn2(mp)3(ox)1/2(H2O)3]n(Ln = Ce(9) and Pr(10)) (op = o-phthalate, ox = oxalate, pma = pyromellitate and mp = m-phthalate), have been prepared, and their photoluminescent properties have been investigated. Compounds 1–6show (3,4)-connected 2D network structures consisting of {Ln(op)}nstaircase chains bridged by ox ligands. Compounds 7and 8consist of 1D zigzag {Dy(ox)}nchains linked by pma ligands adopting a new μ4-hexadentate coordination mode to form 2D 6-connected networks with (36·46·53) topology. Through KO interactions, the 2D networks are further connected to construct 3D structures. Compounds 9and 10display inorganic–organic 3D topology networks with the Schläfli symbol (3·43·52)(32·410·59·614·7)(42·5) containing mixed (3,4,9)-connected nodes. [ABSTRACT FROM AUTHOR]

Three 2D layered zinc coordination polymers: Zn(trz)(HBDC) (1), Zn4(trz)4(4-FBA)4·(H2O)0.5(2) and Zn4(trz)4(4-CBA)4(3) (trz = 1,2,4-triazole, H2BDC = 1,3-benzenedicarboxylic acid, 4-HFBA = 4-fluorobenzoic acid and 4-HCBA = 4-chlorobenzoic acid) have been synthesized by hydrothermal reactions and characterized by IR, elemental analysis, TGA measurements and X-ray single-crystal analysis. Compounds 1–3have the same 2D layer constructed by zinc(ii) with trz and carboxylate. The main difference in the structure of the three compounds is the interactions between the layers. Compound 1shows unusual intermolecular hydrogen bonding and C–Oπ interactions, compound 2exhibits intermolecular hydrogen bonding and C–Fπ interactions, while compound 3only shows intermolecular C–Clπ interactions. It is found that the noncovalent intermolecular interactions have an influence on crystal packing. [ABSTRACT FROM AUTHOR]

Seven lanthanide–organic frameworks [(CeCl 2 L(phen)) 2 (μ-Cl) 2 ]·CH 3 CN ( 1 ) (L = tetrakis(O-isopropyl)methylenediphosphonate, phen = 1,10-phenanthroline) and [LnCl(H 2 O) 3 L(phen)]· n CH 3 CN ( n = 0 for 2 , n = 2 for 3 , n = 1.5 for 4 , n = 0 for 5 , n = 1.5 for 6 , n = 1.5 for 7 ) (Ln = Dy, Ho, Er, Tm, Yb, Lu for 2 – 7 , respectively) have been synthesized by the reaction of lanthanide chlorides, the ligand L and phen in acetonitrile at room temperature. These title complexes were characterized by IR, elemental analyses, single-crystal X-ray diffraction analysis, luminescence, thermal analysis, 1 H NMR and 31 P NMR spectroscopy. The complex [(CeCl 2 Lphen) 2 (μ-Cl) 2 ]·CH 3 CN ( 1 ) is a dinuclear compound and displays a two-dimensional mesh 6 3 topology formed by π – π interactions. Complexes 2 – 7 can be simplified as having a two-dimensional mesh 4.8 2 topology formed by hydrogen bonds (C–H⋯Cl and O–H⋯Cl). These interesting structures are rarely found. We found a fluorescence quenching phenomenon which may be due to the presence of crystalline water molecules and solvent. Their terahertz (THz) time-domain spectroscopy was also studied. [ABSTRACT FROM AUTHOR]

Under the guidance of self-assembly, a series of Cu(I)/Cu(II) metal-organic complexes (MOCs), [Cu3(TCPB)2(H2O)3]·2H2O (1), {[Cu2(TCPB) (DMA)(H2O)]·H2O} n (2), [(Cu8I8) (Cu6I6)0.5(DABCO)3·2H2O] n (3), and [(Cu4I8) (DABCO)2·6H2O]2n (4) (H3TCPB = 1,3,5-tris(4-carbonylphenyloxy)-benzene, DABCO = 1,4-diazabicyclo[2.2.2]octane) have been synthesized and characterized. Complexes 1 and 2 are driven by noncovalent interactions to assemble into supramolecular metal-organic frameworks. Considering H3TCPB ligand with different geometrical structures, 1 forms an Eiffel Tower shaped supramolecular cage based on equilateral triangle shaped trinuclear [Cu3(CO2)3] unit, which possesses effective free volume about 24.7%. Changing the solvent, 2 displays 1D chain structure based on linear bivalent copper trinuclear {Cu3(CO2)2(H2O)2}. When inducing auxiliary ligand DABCO, H3TCPB serves as additive agent and 3 consists of mixed CuI clusters (Cu6I6 and Cu8I8) and plays a 2D layer, which is a rare example. Without additive agent, 4 exhibits a 2D cuprous iodide layer, where 3 and 4 are two novel copper-iodide supramolecular isomers. Owing to large voids in the framework, 1 can serve as a host for use in dye adsorption. The experiment results show that different dyes, including "just right size" Crystal Violet (CV) can be rapidly adsorbed by 1, but smaller Indigo Blue (IB), Methylene Blue (MEB), Methyl Orange (MO), and larger Rhodamine B (RB) and Methyl Blue (MB) can hardly be adsorbed. Surprisingly, 1 also preferentially adsorbs (or separates) CV from MO and CV in their mixed aqueous solution with fast response and high sensitivity (<16.13 s) by the theoretical calculation. Moreover, absorption spectra demonstrate the band gaps of 3 and 4 are 2.37 and 1.98 eV, respectively. When increasing the dimensions of inorganic compositions in cluster-organic complexes, it could exert a remarkable influence on the band gap. [ABSTRACT FROM AUTHOR]

Five novel silver(I) complexes and two copper(I) phosphine complexes containing the bis[2-(diphenylphosphino)phenyl]ether ligand were synthesized and structurally characterized. Treatment of AgX / CuX and the bis[2-(diphenylphosphino)phenyl]ether with N^N ligands afforded the silver(I) or copper(I) complexes {[Ag 2 (POP) 2 (dpa)(H 2 O) 2 ](dpa)(ClO 4 ) 2 } n ( 1 ), {[Ag(POP)(dpp)](ClO 4 )} n ( 2 ), [Ag 2 (POP) 2 (4,4′-bipy)(CH 3 CN) 2 ](CF 3 SO 3 ) 2 ·CH 3 CN ( 3 ), {[Ag(POP)(dpe)](CF 3 SO 3 )·CH 3 CN} n ( 4 ), { [Ag 2 (POP) 2 (dpe)(H 2 O) 2 ](dpe)(BF 4 ) 2 } n ( 5 ), [Cu(POP)(bpy)](BF 4 ) ( 6 ) and [Cu 2 (POP) 2 (4,4′-bipy)](CF 3 SO 3 ) 2 ·4CH 3 CN ( 7 ) {POP = bis[2-(diphenylphosphino)phenyl]ether; dpp = 1,3-bis(4-pyridyl)propane; dpa = 1,2-bis(4-pyridyl)ethane; dpe = 1,2-bis(4-pyridyl)ethene; 4,4′-bipy = 4,4′-bipyridine; bpy = 2,2′-bipyridine}. These complexes are all characterized by IR, elemental analysis, X-ray diffraction, luminescence, 31 P NMR and 1 H NMR spectroscopy. Complex 5 has an irregular (6,3) network structure connected through hydrogen bonds between the C–H groups of aromatic rings and anions; complexes 1 and 2 are of 2D topological architectures which are linked by hydrogen bonds; complex 4 is of a 1D infinite zigzag chain structure formed by the bridging ligand dpe; complexes 3 and 7 are of dinuclear structures and complex 6 is of mononuclear structure. The choice of solvent and the type and coordination modes of the bipyridine derivatives are of importance in defining the structural and topological features of the resulting networks. In addition, the complexes 1 – 7 exhibit interesting luminescence in the solid state at room temperature. At the same time, we also studied the terahertz spectrum which provided some new informations of these complexes. [ABSTRACT FROM AUTHOR]

The reactions of 1,3-bis(diphenylphosphino)propane (dppp) and 1,10-phenanthroline derivative with Ag salts in the mixed solvent of methanol and dichloromethane generate the corresponding complexes, {[Ag 2 (dppp) 2 (phen) 2 ](BF 4 ) 2 (H 2 O) 2 } n ( 1 ) (dppp = 1,3-bis(diphenylphosphino)propane), {[Ag 2 (dppp) 2 (dmp) 2 ](CF 3 SO 3 ) 2 } n ( 2 ), {[Ag 2 (dppp) 2 (dmp) 2 ](BF 4 )} n ( 3 ) (dmp = neocuproine), {[Ag 2 (dppp) 2 (Bphen) 2 ](CF 3 SO 3 ) 2 } n ( 4 ) and {[Ag 2 (dppp) 2 (Bphen) 2 ](ClO 4 )} ( 5 ) (Bphen = 4,7-diphenyl-1,10-diazaphenanthrene). All the complexes are characterized by X-ray diffraction, luminescence, 31 P, 1 H NMR spectroscopy and terahertz (THz) spectra. These five complexes are of dinuclear structures. The topological analysis of simplified underlying nets reveals that complexes 1 – 4 have topologically promising architectures formed through hydrogen bonds (F⋯H–C) between the C–H groups of aromatic ring and anions. Thermogravimetric analysis (TGA) shows the complexes 1 – 5 possess good thermal stability up to 300 °C. [ABSTRACT FROM AUTHOR]

The reactions of copper(I) salts CuX [X = Cl, OTf (OTf = CF 3 SO 3 ) and ClO 4 ] and bis(diphenylphosphino)methane (dppm) with 4,4-bipyridine (4,4-bipy), 2,2-bipyridine (2,2-bipy), isoquinoline (i-C 9 H 7 N) and 1,10-phenanthroline (phen) lead to five new copper(I) complexes: [CuCl(dppm)(i-C 9 H 7 N)] 2 ( 1 ), {[CuCl(dppm)(phen)] 2 •5H 2 O} n ( 2 ), [Cu 2 Cl 2 (dppm) 2 (4,4-bipy)]•4CH 3 CN ( 3 ), [Cu(dppm)(2,2-bipy)] 2 (OTf) 2 ( 4 ), {[Cu 2 Cl(dppm) 2 (4,4-bipy)](ClO 4 )} n ( 5 ). Complexes 1 , 3 and 4 are of dinuclear structure with eight-membered Cu 2 P 4 C 2 rings. The structure of compound 2 can be simplified as three-dimensional topology. Complex 5 is of infinite chain structure linked by 4,4-bipy. All these complexes are characterized by IR, elemental analyses, single-crystal X-ray diffraction analysis, luminescence, NMR and terahertz time-domain spectroscopy. [ABSTRACT FROM AUTHOR]

Abstract: A series of lanthanide complexes [LnL(NO3)3]·CH3CN [Ln=Ce, (1•Ce); Nd, (2•Nd); Tb, (3•Tb); Dy, (4•Dy); Ho, (5•Ho); Er, (6•Er); Tm, (7•Tm); Yb (8•Yb)] have been synthesized by the reaction of N4 chelate ligand N,N'-bis(2-pyridinylmethylene)cyclohexane-1,2-diamine (L) with lanthanide salts. Photoluminescence spectra of complexes 2•Nd, 3•Tb, 4•Dy, and 8•Yb show the strong characteristic luminescence from visible to near infrared (NIR) region. Further, the singlet state (32,467cm−1) and the lowest triplet (23,202cm−1) energy level of L are calculated, indicating that the energy transfer from L to Tb3+ ion is more effective than that to Dy3+ ion. An extended work is developed to discuss on the effect of deuterated reagent and temperature on luminescent properties of 3•Tb and 8•Yb. [Copyright &y& Elsevier]

A series of novel lanthanide coordination polymers havebeen successfullysynthesized under hydrothermal or solvothermal conditions, namely,[Eu2(2,4′-bpdc)2(OH)(NO3)(H2O)3]n(1), [Ln(2,4′-bpdc)(1,4-bdc)0.5(DMF)-(H2O)·H2O]n[Ln = Eu (2); Ln = Pr (3); Ln = Nd (4)], [Ln(2,4′-bpdc)(DMF)2NO3]n[Ln = Eu (5); Ln = Nd (6); Ln = Gd (7)], and[Eu(2,4′-bpdc)(2,4′-Hbpdc)(H2O)]n(8), (2,4′-H2bpdc= 2,4′-biphenyldicarboxylic acid, 1,4-H2bdc = 1,4-benzenedicarboxylicacid, and DMF = N,N′-dimethylformamide).X-ray crystallographic studies reveal that 1featuresa three-dimensional (3D) framework with 45topology. 2–4, which are isostructural and synthesizedby using a mixture of 2,4′-H2bpdc and 1,4-H2bdc, exhibit two-dimensional (2D) (3,4)-connected net structures. 5–7show 2D layered structures containingdouble helix chains (Δ and Λ) with 44topology. 8possesses a 2D layered structure containing (4,6)-connectednetworks, which are connected by means of infinite zigzag chains linkedby 2,4′-bpdc2–and 2,4′-Hbpdc–anions. Furthermore, steady-state and time-resolvedspectroscopic measurements reveal that the four Eu(III) complexes, 1, 2, 5, and 8, exhibitremarkable red luminescence emissions with lifetimes at the millisecondscale. Complexes 4and 6display characteristicluminescent properties for Nd(III) in the near-infrared region. Thesinglet state and the lowest triplet level of ligand 2,4′-H2bpdc were calculated on the basis of the UV–vis absorbanceedges of ligand and the phosphorescence spectrum of Gd(III) complex 7. The energy transfer mechanisms in the lanthanide polymersare described and discussed. [ABSTRACT FROM AUTHOR]

Abstract: Three new complexes [Cd(H2pimda)2(H2O)2]·4H2O (1), [Zn(H2pimda)2(H2O)2]·3.5H2O (2) and [Cd2(Hpimda)2(DMF)2] n (3) (H3pimda=2-propyl-1H-imidazole-4,5-dicarboxy acid, DMF= N,N′-dimethylformamide) have been synthesized under hydrothermal or solvothermal conditions, respectively. Crystal structures of complexes 1–3 were determined by single crystal X-ray diffraction. Crystallographic studies on 1 and 2 reveal that both complexes are six-coordinated, whose geometries can be best described as distorted octahedron. Complex 3 was synthesized based on that of complexes 1 and 2. We change the coordination environment of H3pimda during the synthesis process of complex 3 using organic acid and organic solvent, accordingly, result in different structures ranging from 0D molecule (for 1 and 2) to infinite 2D network (for 3). Complexes 1–3 have blue fluorescent emissions at room temperature in the dimethylsulfoxide (DMSO) solution, which indicate they are potential blue luminescence materials. The blue fluorescent emissions of complexes 1–3 are due to the π∗ →π transitions of intra-ligand. [Copyright &y& Elsevier]

Four novel zinc(II) metal-organic frameworks, {[Zn7(trz)6(1,3-bdc)4(H2O)2]·2H2O}n(1), {[Zn7(trz)6(hip)4(H2O)2]·8H2O}n(2), [Zn4(trz)4(Hnip)2(nip)]n(3), and [Zn5(trz)2(Hbtc)4(H2O)4]n(4) (Htrz = 1,2,4-triazole, 1,3-H2bdc = 1,3-benzenedicarboxylic acid, H2hip = 5-hydroxyisophthalic acid, H2nip = 5-nitroisophthalic acid, and H3btc = 1,3,5-benzenetricarboxylic acid), have been hydrothermally synthesized by reaction of Zn salt and Htrz with four different aromatic acids, respectively. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by X-ray powder diffraction, elemental analyses, IR spectra, and TG analyses. The structures of compounds 1and 2are isostructural and feature the 3D structure containing multidimensional intersecting ring channels formed by the interconnection of 2D layers {[Zn7(trz)6]8+}nwith 1,3-bdc (1) or hip (2). Compound 3consists of {[Zn4(trz)4]4+}nlayers with (4, 82) topology arranged in the −ABAB− stacking sequence, which are connected by nip pillars to generate a novel 3D open framework. Compound 4is also in a 3D structure containing 2D layer motifs, which are further linked by btc ligands to complete the structure. There are two different building units [Zn2(trz)2]2+and [ZnO6] within the 2D layers of 4. All of the compounds 1−4exhibit the 3D pillared-layer structures. In the 2D layer motifs of these four compounds, trz ligands connect Zn ions in different coordination modes, which reflect the tendency of the trz ligand to bridge multiple metal sites, and the aromatic carboxylate ligands in compounds 1−4serve as the pillar between the 2D layers, creating the 3D open frameworks. Moreover, these four compounds exhibit emission properties at room temperature in the solid state. [ABSTRACT FROM AUTHOR]