A series of 1-D zinc(II) coordination polymers with 3-D supramolecular networks: synthesis,structural investigation,and NBO analysis

Abstract

N,N′-Bis(pyridin-4-ylmethylene)naphthalene-1,5-diamine (L) acts as a bipyridine analogue linker ligand towards {Zn₇(μ₄-O)₂(OAc)₁₀}, {Zn₂(NCS)₂(OAc)₂}, and {Zn(N₃)₂} nodes and allows construction of three new 1-D coordination polymers, the linear chain [Zn₇(μ₄-O)₂(OAc)₁₀(L)]_n (1), [Zn(NCS)(OAc)(L)]_n (2) in ladder-type geometry and the zigzag chain [Zn(N₃)₂(L)]_n (3). Structural characterization reveals that in 1 acetate anionic ligands connect seven Zn(II) ions through the bridging coordination modes μ₃-η¹,η² and μ₂-η¹,η¹. The resulting heptanuclear node is located on an inversion center and therefore consists of four crystallographically distinct cations; their coordination spheres correspond to distorted octahedra or tetrahedra. The Zn(II) ions in polymer 2 exhibit distorted trigonal bipyramidal {ZnN₃O₂} coordination; μ₂-η¹,η¹ coordinated acetate and terminal thiocyanate ligands lead to inversion-symmetric [Zn₂(NCS)₂(OAc)₂] secondary building units (SBU), which are further linked by the N,N′-bipyridine analogue L. Terminal coordination of two anionic azide ligands and the bridging bipyridine L result in coordination polymer 3, in which the cations adopt distorted tetrahedral {ZnN₄} coordination. In all crystalline solids 1–3, adjacent 1-D chains interact through π–π stacking and non-classical (C???H···O, C???H···π) hydrogen bonds, leading to 3-D supramolecular architectures. Differences in their 3-D arrangement are due to variations in the anionic co-ligands, subtle conformational differences in the semi-rigid linker and the variable coordination sphere about the zinc cations. Thermogravimetric investigations indicate differences in both thermal stability and decomposition mode. Natural bond orbital (NBO) analysis provides a convenient basis for investigating the intramolecular bonding interactions and delocalization effects in these molecular systems. Finally, solids 1–3 exhibit intense luminescence at room temperature.     

Three different structural lead(II) polymers constructed from newly designed chlorophenyl-imidazole dicarboxylate ligands

A 1-D coordination polymer, {[Pb(o-ClPhH₂IDC)₂]·H₂O}_n (o-ClPhH₃IDC = 2-(2-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (1), a 2-D coordination polymer, [Pb₃(p-ClPhIDC)₂(H₂O)]_n (p-ClPhH₃IDC = 2-(4-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (2), and a 3-D polymer, [Pb(p-ClPhH₂IDC)₂]_n (3), have been obtained solvothermally and structurally characterized by elemental analyses, IR, and single-crystal X-ray diffraction. Although they were prepared with similar ligands and Pb²⁺, polymers 1–3 show distinct structures. The X-ray powder diffraction and thermal properties of the polymers have been investigated. The influence of the reaction conditions to the final products and coordination of the organic ligands are discussed.     

Exploratory syntheses,structures, and photoluminescent properties of three lead multi-dimensional frameworks

Three structurally diverse Pb^II coordination complexes, [Pb₃O(OH)(4-sphth)]₂(H₂O) (1), [Pb(3,5-Hdhb)]H₂O (2), and [Pb₃(4-nphth)₂(OH)₂] (3) (4-H₃sphth, 4-sulfophthalic acid; 3,5-H₂dhb, 3,5-dihydroxybenzoic acid; 4-H₂nphth, 4-nitrophthalic acid), were synthesized under hydrothermal conditions. X-ray diffraction analyses reveal that 1 is constructed from [Pb₄O₄] cubanes, based on which ladder-shaped structure is built via 4-H₃sphth bridge. This is the first Pb₄O₄-containing polymer. The Pb₂O₂ units in 2 are bridged by two parallel 3,5-HDHB ligands along the a-axis and two other parallel 3,5-HDHB ligands along the b-axis, forming a 3-D framework. For 3, the crystal structure is built up of a layer motif consisting of corner-sharing pyramidal Pb₃O units, which are linked through Pb corners to form a hexagonal unit. Each PbO₆ polyhedron is connected to three polyhedra (Pb₃O) via sharing an edge (two μ ₃-oxygen atoms) and two faces (three μ ₃-oxygen atoms), thus yielding an infinite 2-D Pb–O–Pb (3,6-net) honeycomb layer. The luminescence of 1–3 demonstrates that they may be good candidates for luminescent materials.     

Syntheses,crystal structures,and photoluminescence of two new coordination polymers derived from dicarboxylate and N-donor ligands

Two metal-organic coordination polymers, [Co(tda)(ip)(H₂O)₂] _n (1) and [Mn(tda)(ip)(H₂O)] _n (2) [H₂tda?=?thiophene-2,5-dicarboxylic acid, ip?=?1H-imidazo[4,5-f][1,10]-phenanthroline], have been synthesized and characterized by elemental analyses, IR, PXRD, and X-ray diffraction. Single-crystal X-ray analyses reveal that 2,5-tda is a bridging ligand, exhibiting two coordination modes to link metal ions: μ₁-η¹?:?η⁰/μ₁-η¹?:?η⁰ and μ₂-η¹?:?η¹/μ₁-η¹?:?η⁰. Compound 1 demonstrates a 1-D structure in which Co²⁺ centers are connected via tda anions into 1-D chains; the chains are further connected via hydrogen-bonding and π?···?π interactions. Compound 2 displays a 2-D structure in which tda connects two Mn ions forming a dinuclear molecule. In 2 the 3-D supramolecular structure arrays through hydrogen-bonding and π?···?π interactions. In addition, photoluminescence for 1 and 2 is also investigated in the solid state at room temperature.     

Synthesis and characterization of a two-dimensional calcium complex with (1,3,4-thiadiazole-2,5-diyldithio)diacetic acid

A two-dimensional coordination polymer {[Ca₂(tzda)₂(H₂O)₄]?·?3H₂O} _n , where H₂tzda is a flexible carboxylate ligand (1,3,4-thiadiazole-2,5-diyldithio)diacetic acid, was synthesized and characterized by X-ray crystallography, IR, TGA and photoluminescence. The results show that there are two crystallographically independent Ca atoms in the structure, which are both seven-coordinate, but with different coordination environments. Two kinds of tzda^2? ligands with identical coordination mode exist in {[Ca₂(tzda)₂(H₂O)₄]?·?3H₂O} _n . The η ²-bridging O3 and O8 atoms link the Ca1 atoms into a 1-D chain, which are further connected by the tzda^2? ligands forming a 2-D network. A series of hydrogen bonds link the 2-D network to form a 3-D architecture. The solid state luminescence behavior of {[Ca₂(tzda)₂(H₂O)₄]?·?3H₂O} _n exhibits one intense emission band at 375?nm upon excitation at 315?nm which can be attributed to the intraligand emission.     

Two lead coordination polymers with nitrilotriacetic acid and oxydiacetic acid: synthesis,characterization, and crystal structure

Two lead coordination compounds [Pb₂(nta)]NO₃ (1) and [Pb(oda)] (2) have been synthesized by slow evaporation or hydrothermal conditions using nitrilotriacetic acid (nta) and 2,2′-oxydiacetic acid (oda) as ligands, respectively. Their structures were determined by single-crystal X-ray diffraction and further characterized by X-ray powder diffraction, infrared absorption spectrum, and thermogravimetric analysis. Compound 1 is a 2-D honeycomb-like layer structure with (6,3) topology. When the bonding limit of Pb–O extends from 2.76 to 2.90 Å, potential weak Pb–O bonds can be found in 1, and the 2-D layer structure can be further linked to generate a 3-D 4-connected supramolecular sra net with the (4².6³.8) Schläfli symbol. Compound 2 contains a 1-D infinite Pb–O chain which is connected through µ₃-, µ₄-, and µ₅-coordination modes of oda to form a new 3-D structure.     

Poly[(N,N‐dimethylformamide‐κO)(μ3‐4,4′‐ethylenedibenzoato‐κ5O,O′:O′:O′′,O′′′)(pyrazino[2,3‐f][1,10]phenanthroline‐κ2N8,N9)lead(II)]

In the title Pb^II coordination polymer, [Pb(C₁₆H₁₀O₄)(C₁₄H₈N₄)(C₃H₇NO)]_n, each Pb^II atom is eight‐coordinated by two chelating N atoms from one pyrazino[2,3‐f][1,10]phenanthroline (L) ligand, one dimethylformamide (DMF) O atom and five carboxylate O atoms from three different 4,4′‐ethylenedibenzoate (eedb) ligands. The eedb dianions bridge neighbouring Pb^II centres through four typical Pb—O bonds and one longer Pb—O interaction to form a two‐dimensional structure. The C atoms from the L and eedb ligands form C—H...O hydrogen bonds with the O atoms of eedb and DMF ligands, which further stabilize the structure. The title compound is the first Pb^II coordination polymer incorporating the L ligand.     

Lead(II) and cadmium(II) complexes of 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine-p,p′-disulfonate with high thermal stability

Pb(II) and Cd(II) complexes, {[Pb₂(PDTS)₂(CH₃OH)((H₂O)₂]? H₂O} _n (1) and [Cd(PDTS)(H₂O)₄]? 2H₂O (2) (PDTS^2? = 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine-p,p′-disulfonate), are synthesized and characterized by elemental analysis, infrared (IR), ¹H-NMR spectroscopy, and thermal analysis. The single-crystal structure of 1 shows that the complex forms a 2-D polymeric network containing two types of Pb²⁺ with coordination number eight (PbN₂O₆). Both possess hemidirected coordination geometries. The single-crystal structure of 2 shows distorted octahedral geometry for cadmium(II), CdN₂O₄. These compounds are the first complexes of “PDTS^2?”. The supramolecular features in these complexes are guided/controlled by hydrogen bonding and noncovalent intermolecular interactions.     

Hydrothermal synthesis,structure, and properties of lead(II)-based coordination compounds with R-isophthalic acid (R=OH,CH3)

Three new lead(II)-based coordination polymers, [Pb(5-OH-BDC)] _n ?·?nH₂O (1) (5-OH-BDC?=?5-hydroxyisophthalate), [Pb₂(5-CH₃-BDC)₂] _n (2), and [Pb₂(5-CH₃-BDC)₂(phen)₂] _n ?·?2nH₂O (3) (5-CH₃-BDC?=?5-methylisophthalate, phen?=?1,10-phenanthroline), have been hydrothermally synthesized, structurally determined by single-crystal X-ray diffraction, and characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Both 1 and 2 exhibit 2-D double-layer network structures, while 3 possesses 1-D chain structure bridged by 5-CH₃-BDC. The coordination sphere of Pb(II) in 1 is holodirected, whereas in 2 and 3 the spheres feature hemidirected structures. Fluorescence properties of 1–3 have been investigated in the crystalline state at room temperature.     

Two complexes based on 1H-1,2,3-triazole-4,5-dicarboxylic acid: hydrothermal synthesis,crystal structures and spectral properties

[Zn₃(tda)₂(bipy)₂(H₂O)_2?·?4H₂O] _n (1) and [Co₂(Htda)₂(H₂O)₆·5H₂O] (2) have been synthesized and characterized structurally by X-ray diffraction, where H₃tda?=?1H-1,2,3-triazole-4, 5-dicarboxylic acid and 2,2′-bipy?=?2,2′-bipyridine. Their solid-state structures have been characterized by elemental analysis and IR spectroscopy. The molecular unit of 1 consists of two crystallographically unique Zn(II) ions assuming different coordination geometries, the tda^3? exhibits a hexadentate binding mode chelating three Zn(II) ions; neighboring Zn–Zn distances through tda^3? bridges are 5.910(6), 5.888(5), and 6.279(3)?Å, respectively. In 2, two neighboring Co(II) ions are bridged by two Htda^2? ligands, forming a binuclear structure, with Co–Co distance of 4.091?Å and is further linked to generate a 3-D structure via hydrogen bonds. Fluorescent of 1 was investigated.     

Two new Pb(II) coordination polymers derived from fatty dicarboxylates and phenanthroline derivatives: syntheses,structures, and properties

Two new Pb(II) coordination polymers, [Pb(3-pdip)(L₁)]?·?0.5H₂O (1) and [Pb(4-pdip)(L₂)] (2) [L₁?=?heptane diacid, L₂?=?hexane diacid, 3-pdip?=?2?-(3-pyridyl)imidazo[4,5-f]1,10-phenanthroline, 4-pdip?=?2?-(4-pyridyl)imidazo[4,5-f]1,10-phenanthroline], have been obtained from hydrothermal reactions of Pb(II) nitrate with two flexible fatty carboxylic acids and two phenanthroline derivatives. Single-crystal X-ray diffraction analysis reveals that 1 is a 1-D staircase-like double chain coordination polymer extended by binuclear [Pb₂N₄O₈] subunits and pairs of L₁ ligands. Compound 2 exhibits a 2-D (4,4) network based on bi-metallic [Pb₂N₆O₈] units and (L₂)₂/(4-pdip)₂ double linkers. Furthermore, adjacent chains of 1 and layers of 2 are extended into 3-D supramolecular networks by π–π stacking interactions between aromatic rings of phenanthroline groups. The organic carboxylic acids with different lengths show great influence on the shapes of Pb(II)-carboxylate double chains. Phenanthroline derivatives possessing different sites of N-donors (3-pyridyl and 4-pyridyl) determine the final coordination frameworks of 1 and 2. Photoluminescence and thermal stabilities of 1 and 2 were also investigated.     

Effect of solvent on the construction of Co(II) coordination polymers containing a semi-rigid bis(benzimidazole) derivative: syntheses,structures, and properties

Two Co(II) coordination polymers, [CoL(npa)]·2H₂O (1) and [CoL(Hnpa)₂] (2) (L = 1,4-bis(5,6-dimethylbenzimidazole-1-yl)benzene, H₂npa = 5-nitroisophthalic acid), have been synthesized in different solvent systems and characterized by Infrared (IR) spectroscopy, elemental analysis, and powder and single crystal X-ray diffraction. Compound 1 was synthesized under solvothermal conditions with DMF as solvent and had a pair of L ligands adopting a μ₂-bridging mode and connecting two Co²⁺ cations to generate a 26-membered Co₂L₂ loop. The npa^2? link adjacent Co₂L₂ loops via a bis(monodentate) bridging mode to create a 1-D channel-like chain structure. Compound 2 was obtained under hydrothermal conditions, and the carboxylate of the monodeprotonated Hnpa^? adopt a μ₁-η^0?:?η¹ coordination to connect adjacent Co²⁺ cations into a 2-D polymeric layer. The μ₂-bridging L ligands connect adjacent 2-D [Co(Hnpa)]_n polymeric layers into a 3-D NaCl-like framework. The Co²⁺ cations and the L ligands in compounds 1 and 2 exhibit different coordination geometries and conformations. Effects of solvents on the construction of Co(II) coordination polymers were investigated. In addition, the electrochemical behavior of carbon paste electrodes containing 1 and 2 and the thermal stabilities of 1 and 2 were investigated.     

1-D chain Cd(II) compound based on flexible phenylenediacetic ligand: synthesis,crystal structure,and fluorescent properties

A coordination polymer of Cd^II with a flexible ligand in [Cd(Hpda)₂(4,4′-bipyridyl)₂]?·?(H₂O)₂ (1) (H₂pda?=?1,2-phenylenediacetic acid) has been synthesized by hydrothermal reactions and characterized by IR, TG, fluorescent spectrum, X-ray powder diffraction, and single-crystal X-ray diffraction techniques. The results show that 1 is monoclinic, with space group P2(1)/c, a?=?1.1704(7), b?=?1.7206(1), and c?=?2.2073(1) nm, β?=?120.881(2)°. In 1, the Cd(II) ions are linked by 4,4′-bipyridyl ligands to form 1-D chain with the arms of 1,2-pda ligands. These chains are imbedded into each other to form 2-D supramolecular sheets through hydrogen bonds. Adjacent 2-D sheets are assembled to 3-D network architecture through the crystallization of water molecules. Photoluminescence properties of 1 were investigated in the solid state at room temperature. The spectrum shows intense photoluminescence at 300?nm (λ_ex?=?275?nm).     

Structures and luminescent properties of four compounds based on binuclear metal-terpyridine building blocks

Four new coordination polymers, [Cd(3-TPTP)Cl]₂ (3-HTPTP = 4′-(3-tetrazolylphenyl)2,2′:6′2′′-terpyridine, 1), {[Cd(3-TPTP)(pBDC)_0.5]?4H₂O}_n (pH₂BDC = 1,4-benzenedicarboxylic acid, 2), {[Mn(3-TPTP)(mBDC)_0.5]?5H₂O}_n (mH₂BDC = 1,3-benzenedicarboxylic acid, 3), and [Pb(3-TPTP)(H₂O)₂]?OH (4), were obtained. Compounds 1–3 are composed of binuclear [M₂(3-TPTP)₂] ring as building unit. In 1, the binuclear rings pack into a 3-D supramolecular framework via various hydrogen bonds. In 2 and 3, the binuclear rings are connected by mBDC^2? and pBDC^2?, respectively, resulting in two types of 1-D chains. In 4, the mononuclear [Pb(3-TPTP)] units are connected by Pb?N weak interactions, giving a chiral 1-D coordination chain, which is further connected by O–H?N interaction to form a chiral 3-D supramolecular framework. The phase purity of 1–4 and luminescence properties of 1, 2, and 4 were also investigated.     

Three new coordination frameworks based on 2-ethyl-imidazole-4,5-dicarboxylate and 1,10-phenanthroline: syntheses,crystal structures,and luminescence

Three new coordination polymers based on 2-ethyl-imidazole-4,5-dicarboxylate with 1,10-phenanthroline as ligands, Pb(HEIDC)(phen)₂ (1), [Zn(EIDC)(phen)] _n (2), and {[Ba(H₂EIDC)₂(phen)]?·?(phen)₂?·?[Ba(H₂EIDC)(HEIDC)(phen)]} _n (3) (H₃EIDC?=?2-ethyl-1-Himidazole-4,5-dicarboxylate; phen?=?1,10-phenanthroline), have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Complex 1 displays a tetranuclear square constructed of four Pb(II) centers, four HEIDC, and eight phen, resulting in a 3-D network with a 1-D open channel along the c-axis via C–H?···?O hydrogen bonds, C–H?···?π, and π–π stacking interactions. Complex 2 is an infinite zigzag chain resulting in the final 3-D supramolecular framework via C–H?···?O and π–π stacking interactions. Complex 3 is composed of two individual Ba chains, exhibiting a 3-D framework via O–H?···?O, O–H?···?N hydrogen bonds, and π–π stacking interactions. The photoluminescence spectra of 1 and 2 in the solid state have been investigated, 1 exhibits green photoluminescence in the solid state at room temperature.     

A holodirected Pb(II) architecture based on bifunctional tetrazole-carboxylate and photoluminescence

A new 1-D Pb(II) complex {[Pb₂(H₂O)₄(tppbc)₂]?·?(CH₃)₂NCHO} _n (1) based on tetrazole-carboxylate bifunctional ligand has been prepared and characterized (tppbc?=?3-(4-(2-(1H-tetrazol-5-yl)phenyl-4-yl)phenyl)-2-ethoxy-3H-benzimidazole-4-carboxylic acid). Photo-luminescence measurements indicate that although the fluorescence of tppbc is quenched after coordination, the Pb(II) complex shows strong intense phosphorescence emission. Lifetimes at 298?K and low temperatures agree with the large Stokes shift of 1.     

Synthesis and crystal structures of two lead(II) complexes of 4,4,4-trifluoro-1-naphthyl-1,3-butanedione ligand,subtle interplay of weak intermolecular interactions

[Pb₂(tfnb)₄ (µ-CH₃OH)] _n (1) and [Pb₂(dmp)₂(tfnb)₄] (2) (tfnb and dmp are the abbreviations for 4,4,4-trifluoro-1-naphthyl-1,3-butanedionate and 2,9-dimethyl-1,10-phenanthroline) have been synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, and thermal analysis. The single-crystal structure of 1 shows that the complex forms two 1-D polymeric networks containing four types of Pb²⁺ with coordination numbers seven for Pb(1) and Pb(3), five for Pb(2), and six for Pb(4). The single-crystal structure of 2 shows that the complex forms a dinuclear complex with eight-coordinate Pb(II). The supramolecular features in this complex are guided by lone-pair activity and the control of weak directional intermolecular interactions and aromatic π–π stacking interactions.     

Solid‐State Structural Transformations and Photoreactivity of 1D‐Ladder Coordination Polymers of PbII

An attempt has been made to design double‐stranded ladder‐like coordination polymers (CPs) of hemidirected Pb^II. Four CPs, [Pb(μ‐bpe)(O₂C‐C₆H₅)₂] ? 2H₂O ( 1 ), [Pb₂(μ‐bpe)₂(μ‐O₂C‐C₆H₅)₂(O₂C‐C₆H₅)₂] ( 2 ), [Pb₂(μ‐bpe)₂(μ‐O₂C‐p‐Tol)₂(O₂C‐p‐Tol)₂] ? 1.5 H₂O ( 3 ) and [Pb₂(μ‐bpe)₂(μ‐O₂C‐m‐Tol)₂(O₂C‐m‐Tol)₂] ( 4 ) (bpe=1,2‐bis(4′‐pyridyl)ethylene), have been synthesised and investigated for their solid‐state photoreactivity. CPs 2 – 4 , having a parallel orientation of bpe molecules in their ladder structures and being bridged by carboxylates, were found to be photoreactive, whereas CP 1 is a linear one‐dimensional (1D) CP with guest water molecules aggregating to form a hydrogen‐bonded 1D structure. The linear strands of 1 were found to pair up upon eliminating lattice water molecules by heating, which led to the solid‐state structural transformation of photostable linear 1D CP 1 into photoreactive ladder CP 2 . In the construction of the double‐stranded ladder‐like structures, the parallel alignment of C?C bonds in 2 – 4 is dictated by the chelating and μ₂‐η²:η¹ bridging modes of the benzoate and toluate ligands. The role of solvents in the formation of such double‐stranded ladder‐like structures has also been investigated. A single‐crystal‐to‐single‐crystal transformation occurred when 4 was irradiated under UV light to form [Pb₂(rctt‐tpcb)(μ‐O₂C‐m‐Tol)₂(O₂C‐m‐Tol)₂] ( 5 ).     

Synthesis,structures and thermal stabilities of three 1-D coordination polymers based on flexible polycarboxylates

Three new coordination polymers, [Cu(butca)_0.5(bipy)(H₂O)] _n · 2nH₂O (1), [Zn(H₂butca) (phen)(H₂O)] _n · nH₂O (2), and [Cd(H₂chhca)_0.5(phen)(H₂O)] _n · 2nH₂O (3) (H₄butca =1,2,3,4-butanetetracarboxylic acid, H₆chhca = 1,2,3,4,5,6-cyclohexanehexacarboxylic acid), were prepared and characterized by EA, IR, TG, and X-ray crystallography. Complex 1 is a 1-D double-chain coordination polymer in which tetradentate butca^4? coordinates to four Cu(II) ions through four monodentate carboxylates. Complex 2 is a 1-D chain with tridentate H₂butca^2? coordinating to two Zn(II) ions through monodentate and chelating carboxylates. Complex 3 is a 1-D double-chain coordination polymer. H₂chhca^4? is octadentate coordinating to four Cd(II) ions through four chelating carboxylates. Hydrogen bonds and π–π stacking interactions play important roles in the formation of supramolecular architectures. The thermal stabilities of 1–3 show dehydrated coordination polymers are thermally stable in the range 260–400°C.     

Synthesis and characterization of Pb(II) compounds constructed from N-tosyl-L-glutamic acid

{[Pb(tsgluo)]?·?H₂O} _n (1), [Pb₂(tsgluo)₂(phen)₂] (2), and [Pb₂(tsgluo)₂(bipy)₂] (3) (H₂tsgluo?=?N-p-tolylsulfonyl-L-glutamate, phen?=?1,10-phenanthroline, bipy?=?2,2′-pyridine) have been synthesized in the absence or presence of phen or 2,2′-bipy and structurally characterized by elemental analysis, IR, and X-ray crystallography. Single-crystal X-ray analyses reveal that tsgluo exhibits two coordination modes to link lead ions. Complex 1 gives a 2-D layer structure while 2 and 3 exhibit monomolecular structures; 3 is further connected into a double-chain structure by hydrogen bonds. Phen and 2,2′-bipy are very important for the crystal structure. Fluorescence of the compounds is also discussed.