Tib Ligands Research Articles

Construction of coordination polymer [Ni(ppda) (tib) (H2O)]·H2O and photocatalytic degradation of indigo carmine

Semiconductor coordination polymers have garnered significant attention as photocatalysts for wastewater treatment owing to their adaptable structure, expansive specific surface area, and outstanding selectivity, stability, and sensitivity. In this study, coordination polymer [Ni(ppda) (tib) (H2O)]·H2O was synthesized utilizing flexible phenyldiacetic acid (H2ppda) and rigid 1,3,5-tris(1-imidazolyl)benzene (tib). Crystal structure analysis revealed that the three-linked tib ligands and the central Ni(II) ion create a wavy 2D surface. Additionally, cis-ppda2- ligands form a 1D wave chain alongside central Ni(II), which traverse through a 2D layer. Adjacent layers are interlaced via ppda2−, resulting in a complex 3D supramolecular structure. The fundamental framework of [Ni(ppda) (tib) (H2O)]·H2O exhibits stability up to 316 °C and remains stable over 5 cycles, with a band gap energy of 2.9 eV, rendering it a viable candidate for catalytic applications. In aqueous systems, [Ni(ppda) (tib) (H2O)]·H2O demonstrates efficient photocatalytic degradation of Indigo Carmine (IC), achieving a degradation rate of 98.5% and a reaction rate of 0.027 min−1, showcasing commendable selectivity and semiconductor properties. The primary photocatalytic degradation mechanism involves the synergistic formation of ·OH and ·O2- active species through the interaction between [Ni(ppda) (tib) (H2O)]·H2O and H2O2, facilitating the oxidative degradation of dye molecules.

Three novel MOFs constructed from 1,3,5-tris(1-imidazolyl)benzene and dicarboxylate ligands with selective adsorption for C2H2/C2H4 and C2H6/CH4.

The urothermal reactions of Co(II)/Zn(II) salts with the diverse carboxylic acid and 1,3,5,-tris(1-imidazolyl)benzene(tib) ligands afforded three novel MOFs, namely, [Co3(tib)2(abdc)2(ox)]2·6H2O (1), [Co3O(tib)(abdc)2(DMI)]·2DMI·2H2O (2) and [Zn3I2(tib)2(napdc)2]·2DMI·2H2O (3), (H2abdc = 5-amino-1,3-benzenedicarboxylate, H2napdc = 1,4-naphthalene dicarboxylic acid and DMI = 1,3-dimethyl-2-imidazolidinone). In compounds 1 and 2, the Co(II) atoms are connected by polycarboxylate ligands to form two-dimensional (2D) layers that are pillared by tib ligands leading to the formation of 3D porous frameworks. In compound 3, the Zn(II) atoms are linked by tib ligands to form one-dimensional ribbon-like chains which are further connected by polycarboxylate ligands, making a 3D framework possible. Compound 1 can selectively adsorb unsaturated hydrocarbon molecules (C2H2 and C2H4) and saturated hydrocarbon molecules (C2H6 and CH4). Specifically, compound 1 has high IAST selectivity for acetylene and methane (0.50 : 0.50, v/v) at 273 K and 1 bar. DFT calculations reveal that the π-conjugated hexagonal carbon ring may be the primary adsorption site because there are π-π interactions between the unsaturated hydrocarbon molecules (C2H2 and C2H4) and the π-conjugated hexagonal carbon ring in the framework of compound 1.

Bromine heavy-atom induced persistent room temperature phosphorescence of [ZnBr2] based coordination polymer

Molecule-based room temperature phosphorescence (RTP) materials have attracted considerable attention owing to their extensive applications in the optoelectronic and biological field. In this paper, two isostructural coordination polymers [Zn3(TIB)2X6] (X ​= ​Cl, 1-Cl; X ​= ​Br, 1-Br) have been synthesised and characterized by the assemble of triangular D-A-D ligand 1,3,5-tri(1H-imidazol-1-yl)benzene (TIB) and ZnX2 salts. The incorporation of halogen atoms play significant role in the formation of abundant C-H···X hydrogen-bonding interactions and dense structures, enable high thermal stability of the two complexes. 1-Br shows phosphorescence lifetime three order of magnitude longer than that of 1-Cl, and obviously phosphorescence emission recognized by naked eyes. The theory calculations reveal complete separation of molecular orbitals between halogen atoms and TIB ligand. Photoelectron response performance have also been studied. This work provides an efficient way to achieve long-last RTP by the incorporation of metal-bromide units in the coordination polymers.

CRYSTALLOGRAPHIC ANALYSIS OF A SAMARIUM(III) COMPLEX WITH 1,3,5-TRIS(1-IMIDAZOLYL)BENZENE

In this paper, a new samarium(III) complex with 1,3,5-tris(1-imidazolyl)benzene(tib) was synthesized via the solvent thermal reaction. The single crystal of the complex is measured by X-ray diffraction and subjected to crystallographic and conformational analyses. The crystal is monoclinic: a = 8.5589(12) A, b = 12.2883(14) A, c = 21.109(3) A, α = 90°, β = 98.585(4)°, γ = 90°, V = 2195.3(5) A3, space group P21/n, Z = 4, ρc = 2.044 mg/m3, R = 0.0513. The asymmetric unit contains one samarium(III) center, eight O atoms from nitrate ions in solvent, and two N atoms from two different tib ligands.

Co(II) and Cu(II) coordination polymers: Crystal structures and treatment effect on acute lung injury treatment by inhibiting inflammatory response

Two coordination polymers named [Co(tib)(H2O)3]· ipa·2H2O (1, H2ipa = iso-phthalic acid) and [Cu3(tib)2(BTB)2]·DMF·2H2O (2, H3BTB = 4,4′,4′′-gbenzene-1,3,5-triyl-tribenzoic acid, DMF = N,N-dimethylformamide) were constructed using a solvothermal method by reaction of metal salts with the 1,3,5-tris(1-imidazolyl)benzene (tib) ligands and different carboxylate linkers as the co-ligands. The two complexes have been characterized by X-ray diffraction as well as the elemental analyses. Subsequently, the protective effect of compounds 1 and 2 on the acute lung injury and its related mechanism was explored. Firstly, the enzyme linked immunosorbent assay (ELISA) was performed to detect the release of the inflammatory cytokines. Then, the partial pressure of oxygen (PaO2) and the partial pressure of carbon dioxide (PaCO2) was measured with blood gas analysis.

Crystallographic analysis of a samarium(III) complex with 1,3,5-tris(1-imidazolyl)benzene

In this paper, a new samarium(III) complex with 1,3,5-tris(1-imidazolyl)benzene(tib) was synthesized via the solvent thermal reaction. The single crystal of the complex is measured by X-ray diffraction and subjected to crystallographic and conformational analyses. The crystal is monoclinic: a = 8.5589(12) Å, b = 12.2883(14) Å, c = 21.109(3) Å, α = 90°, β = 98.585(4)°, γ = 90°, V = 2195.3(5) Å3, space group P21/n, Z = 4, ρc = 2.044 mg/m3, R = 0.0513. The asymmetric unit contains one samarium(III) center, eight O atoms from nitrate ions in solvent, and two N atoms from two different tib ligands.

A 2D Co(II) coordination polymer based on 1,3,5-tris(1H-imidazol-1-yl)benzene: photocatalytic properties and theoretical analysis

A new 2D Co(II) based coordination polymer (CP), {[Co2(tib)2(NO3)3(H2O)2·NO3]n (1), has been synthesized using 1,3,5-tris(1-imidazolyl)benzene (tib) ligand. The single crystal X-ray diffraction study indicates that 1 possesses an infinite 2D layer, which is further extended into a 3D supramolecular network via O–H···O hydrogen bonding interactions. Additionally, the thermogravimetric analysis (TGA) of CP indicates its decomposition temperature was about 268 °C. The UV/Vis diffuse-reflection spectrum of 1 indicates its semiconducting nature on the basis of which the photocatalytic properties of 1 against photodecomposition of organic dyes have been studied. The possible mechanism associated with the photocatalytic activity of 1 against organic dyes is addressed using density of states (DOS) calculations.

PH-Directed assembly of four polyoxometalate-based supramolecular hybrids by using tritopic bridging ligand 1, 3, 5-tris-(1-imidazolyl)-benzene: Structures and electrocatalytic properties

Four new inorganic-organic supramolecular compounds, namely, (H2tib)2[GeW12O40] (1), [Mn(Htib)4][HGeW12O40]2·4H2O (2), [Mn(tib)]2(H2O)6[GeW12O40]·4H2O (3) and [Mn(tib)]2(H2O)6[GeW12O40]·2H2O (4) (tib = 1, 3, 5-tris-(1-imidazolyl)-benzene), have been synthesized through the hydrothermal reaction of [GeW12O40]4- anions, MnII cations and tib ligands under different pH conditions. Compounds 1 and 2 were prepared at lower pH (pH ≈ 2.0 for 1 and 3.2 for 2). Compound 1 exhibits a simple monomer structure. In 2, the Mn cation is coordinated with four tib ligands and two [GeW12 O40]4- anions to form a dimer, in which each of [GeW12 O40]4- anion connects with one Mn cation. Compounds 3 and 4 were prepared at higher pH (pH ≈ 4.2 for 3 and 4.9 for 4), and compounds 3 and 4 display a one-dimensional (1D) chain and a (4, 4)-connected 2D wave-like layer, respectively, and in compound 3, each of GeW12 cluster connects two Mn atoms, however, compound 4: each of GeW12 cluster connects four Mn atoms. The isolation of these four compounds is very informative for systematically understanding the effect of the pH on assembly of polyoxometalate-based hybrids. Also, the electrocatalytic properties of 1–4-CPEs towards nitrite have also been investigated.

A Zn-tib porous framework sandwiched with Keggin Synthesis, structure, photocatalytic and luminescent properties

A novel helical compound, Zn(Htib)(tib)PMo12O40 (1) (tib = 1, 3, 5-tris-(1-imidazolyl)-benzene) was hydrothermally synthesized. The structure has been determined by single-crystal X-ray diffraction analyses and characterized by IR, XPS, UV–Vis and XRD and elemental analyses. Single crystal X-ray analysis reveals that compound 1 possesses entangled double helixes, which is formed by a pair of right- and left- handed double helixes sharing Zn atoms and a part of tib ligands. The adjacent entangled double helixes are further fused together, and thus a wavy Zn-tib metal-organic layer is constructed. Finally, through hydrogen bonds, the neighboring Zn-tib metal-organic layers are interconnected in a staggering peak-load manner to give birth to a porous 3D supramolecular framework with large rhombus-like apertures, in which the [PMo12O40]3- (PMo12) anions were encapsulated into the open channel structure and sandwiched by the Zn-tib layers. Additionally, compound 1 exhibits high efficiency and stability, and well reproducibility towards photocatalytic degradation of RhB dye under UV irradiation. The fluorescence property of 1 was also investigated.

Effect of anions on the self-assembly of two Cd–organic frameworks: syntheses, structural diversity and photoluminescence properties

By employing a rigid tripodal ligand 1,3,5-tris(1-imidazolyl)benzene (tib) to assemble with two different Cd(II) salts, we have obtained two distinct cationic metal–organic frameworks, [Cd(tib)2·2NO3·4DMF]n (1) and [Cd(tib)2·2ClO4·4DMF]n (2) (DMF = N,N-dimethylformamide). The compounds were structurally characterized by single-crystal X-ray diffraction analyses and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). Both compounds 1 and 2 are constructed based on 2D square lattice (sql) nets, through ligand-to-axial (L–A), pillared by triangular tib ligands, resulting in two diverse 3D pillar-layered architectures. Compound 1 features a cationic framework with a (3,6)-connected rtl topology and has rhomboid channels; while for 2, the 2D layers repeat in an ⋯ABAB⋯ staggered stacking mode pillared by tib ligands, resulting in a different cationic framework from 1 with a pyr net. The results demonstrate that counterions NO3− and ClO4− play an important role in the fabrication of structures of 1 and 2. Furthermore, the photoluminescence of compounds 1 and 2 have been investigated in the solid state at ambient temperature.

One pot synthesis, crystal structures and properties of two new MOFs with imidazole-containing tripodal ligand

Two new different Cu(II) MOFs with the same 1,3,5-tris(1-imidazolyl) benzene (tib) ligand {[Cu(tib)2]·(H2O)2·Br2} n (1) and {[Cu2(tib)·Br·Cl]·2Br} n (2) were obtained by one pot synthesized of tib with CuBr in the presences of HCl and water. X-ray single crystal diffraction analyses indicate that both complexes 1 and 2 have two dimensional frameworks containing different building blocks. Each Cu(II) atom in complex 1 is coordinated by four N atoms from different tib ligands. However, there are two different cryptographic Cu(II) atoms in complex 2, one is four coordinated by two bromine atoms and two N atoms from different tib ligands, the other is six coordinated by two chloride atoms and four N atoms from different tib ligands. The thermal gravimetric analysis of complexes 1 and 2 are depicted in the paper.

Imidazole-based zinc(II) complexes: Highly selective fluorescent probes for acetone detection

Two ZnII coordination polymers (Zn-CPs), [Zn(dib)(CH3COO)2]·2H2O (1) and Zn3(tib)2Cl6 (2), have been prepared under hydrothermal condition by reactions of 1,4-di(1H-imidazol-1-yl)benzene (dib), or 1,3,5-tri(1H-imidazol-1-yl)benzene (tib) with corresponding ZnII ions, respectively. Single crystal structure analysis reveals that 1 contains one-dimensional chains, which are further connected into a three-dimensional network by hydrogen bonds and π⋯π interactions. Compound 2 adopts a three-dimensional (3D) supramolecular network which is constructed by one-dimensional (1D) chain via weak Van der Waals force based on Zn(II) ions and tib ligands. These compounds are further characterized by powder X-ray diffraction, element analyses, and photoluminescent spectroscopy. The luminescent properties of 1 and 2 dispersed in different solvents have been investigated systematically. Both of them exhibit a solvent-dependence luminescent behavior and high sensitivity for acetone detection via a fluorescence quenching mechanism.

New Structural Topologies in a Series of 3d Metal Complexes with Isomeric Phenylenediacetates and 1,3,5-Tris(1-imidazolyl)benzene Ligand: Syntheses, Structures, and Magnetic and Luminescence Properties

In this article we present the syntheses, characterizations, magnetic and luminescence properties of five 3d-metal complexes, [Co(tib)(1,2-phda)]n·(H2O)n (1), [Co3(tib)2(1,3-phda)3(H2O)]n·(H2O)2n (2), [Co5(tib)3(1,4-phda)5(H2O)3]n·(H2O)7n (3), [Zn3(tib)2(1,3-phda)3]n·(H2O)4n (4), and [Mn(tib)2(H2O)2]n·(1,4-phdaH)2n·(H2O)4n (5), obtained from the use of isomeric phenylenediacetates (phda) and the neutral 1,3,5-tris(1-imidazolyl)benzene (tib) ligand. Single crystal X-ray structures showed that 1 constitutes 3,5-connected 2-nodal nets with a double-layered two-dimensional (2D) structure, while 2 forms an interpenetrated 2D network (3,4-connected 3-nodal net). Complex 3 has a complicated three-dimensional structure with 10-nodal 3,4,5-connected nets. Complex 4, although it resembles 2 in stoichiometry and basic building structures, forms a very different overall 2D assembly. In complex 5 the dicarboxylic acid, upon losing only one of the acidic protons, does not take part in coordination; instead it forms a complicated hydrogen bonding network with water molecules. Magnetic susceptibility measurements over a wide range of temperatures revealed that the metal ions exchange very poorly through the tib ligand, but for the Co(II) complexes the effects of nonquenched orbital contributions are prominent. The 3d10 metal complex 4 showed strong luminescence with λmax = 415 nm (for λex = 360 nm).

PH-dependent assembly of metal–organic hybrid compounds based on octamolybdates and a new flexible multidentate ligand

Six novel molybdenum hybrid materials based on a flexible multidentate ligand, namely (H3tib)4(β-Mo8O26)3·5H2O (1), (H3tib)2[Cu(H2O)2(γ-Mo8O26)2]·2H2O (2), [Cu(Htib)2(δ-Mo8O26)]·4H2O (3), [Cu2(tib)2(H2O)2(γ-Mo8O26)]·H2O (4), (H3tib)2[Co(H2O)2(γ-Mo8O26)2]·2H2O (5), and Zn(tib)(MoO4)·3H2O (6) (where tib = 1,3,5-tris(imidazol-1-ylmethyl)benzene), have been synthesized at different pH values under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analysis and further characterized by PXRD, TGA, IR spectra, and electrochemistry. Compound 1 is a supramolecule with classical β-Mo8O26 cages. Compounds 2 and 5 exhibit a rare one-dimensional (1D) molybdenum oxide duplex chain. We have not yet found any other examples of the two adjacent 1D molybdenum oxide chains linked together through the centers of the Cu/Co cations. In 3, the CuII cations are bridged by Htib+ ligands and (δ-Mo8O26)4− anions to form an interesting two-dimensional (2D) layer. In 4, the CuIIcations, tib ligands and (γ-Mo8O26)4− anions are connected to form a 2D layer, which is further reinforced by the tib ligands through an Mo–N bond. Compound 6 is a 2D coordination polymer possessing a high thermal stability. The structural diversities of 2–4 reveal that the pH value of the reaction system, the metal coordination preference and the ligand configuration play a crucial role in the assembly of POM-based complexes.

Reactant ratio-modulated entangled Cd(ii) coordination polymers based on rigid tripodal imidazole ligand and tetrabromoterephthalic acid: interpenetration, interdigitation and self-penetration

By adjusting the molar ratio of the reactant metal salt and ligands, three new entangled coordination polymers, [Cd(tib)(tbta)(H2O)]n (1) and [Cd(Htib)(tbta)·Htbta·2CH3OH]n (2) and [Cd2(tib)2(tbta)2(H2O)·10H2O]n (3) (tib = 1,3,5-tris(1-imidazolyl)benzene and H2tbta = tetrabromoterephthalic acid), have been prepared and structurally characterized by X-ray diffraction analyses. Complex 1 is a 2-fold interpenetrated three-dimensional (3D) 8-connected uninodal net with rare hex topology. Complex 2 presents a 2D 63-hcb network, which is interdigitated with each other to form the 3D supramolecular framework stabilized hydrogen bonds and halogen bonds. Interestingly, an unprecedented hydrogen-bonded [(Htbta)2(CH3OH)4] cluster was unmasked in the void of 2. Complex 3 is a complicated 3D self-penetrated framework with a point symbol of {4·6·8}{4·65·84}{66}, which can be seen as a pair of 2-fold interpenetrated networks by breaking bidentate-bridging tib ligand. The comparative study revealed that 1–3 are particularly sensitive to the metal–ligand ratio in this system. The thermal stabilities and photoluminescence behaviors of 1 and 2 were also discussed.

Two polyoxomolybdate-tuned hybrids composed of tripodal star-like ligand copper complexes

Two POM-tuned hybrids containing tripodal star-like ligand copper complexes, [CuII3(H2O)5(tib)2(P2Mo5O23)]·2H2O (1) and [CuI2(Htib)2(PMo11VIMoVO40)]·H2O (2) (tib=1,3,5-tris(1-imidazolyl)benzene), have been hydrothermally synthesized. In compound 1, a 2D wave-like layer is constructed from concave belts bridged by P2Mo5 polyoxoanions in a “hand-in-hand” mode, extending to a 3D supramolecular framework via hydrogen bonding interactions. Compound 2 shows a 1D ladder-like chain formed by [Cu(tib)] chains acting as two sides of the ladder and PMo12 anions acting as middle rails, resulting in a 3D supramolecular structure through hydrogen bonding interactions. The steric hindrance of polyoxoanions, the valence states of copper ions and the coordination modes of tib ligands co-affect together the final structures of title compounds. The electrochemical properties of compounds 1 and 2 are investigated.

Unprecedented three-dimensional 10-connected bct nets based on trinuclear secondary building units and their magnetic behavior

Three unprecedented metal-organic frameworks [M3(tib)2(CTC)2]·nH2O [M = Co(II), n = 2 (1); Mn(II), n = 2.92 (2) and Ni(II), n = 2 (3)] based on M3(OCO)6 trinuclear secondary building units (SBUs) have been successfully synthesized by reactions of corresponding metal salt with mixed flexible triacid of 1,3,5-cyclohexanetricarboxylic acid (H3CTC) and rigid imidazol-containing ligand 1,3,5-tris(1-imidazolyl)benzene (tib) under hydrothermal conditions. In 1–3, the CTC3− ligands link the SBUs to form two-dimensional (2D) ‘hxl’ (hexagonal lattice) networks and the tib ligands further pillar the 2D layers leading to the formation of three-dimensional frameworks, which are firstly reported uninodal 10-connected bct nets. The magnetic measurements showed that 1 and 3 exhibit ferromagnetic coupling interactions between the adjacent metal centers with g = 2.63, D = 66.69 cm−1, zJ = 0.68 cm−1 and g = 2.22, J = 6.25 cm−1, zj′ = −0.053 cm−1, respectively, while 2 has antiferromagnetic interaction between the Mn(II) ions with g = 2.01, J = −0.57 cm−1, zj′ = 1.3 × 10−4 cm−1.

Syntheses, crystal structures and magnetic properties of three novel cobalt(ii) complexes containing imidazole derivative groups

Three Co(II) complexes with the formulas: {[Co2(Bib)3Cl2]Cl(CH3COO)}.CH3OH.H2O (1), [Co2(Bib)3Cl2]Cl2.(CH3OH)2.H2O, (2) and [Co3K1(Tib)2(CH3COO)6]PF6 (3), were obtained by self-assembly of a cobalt(II) salt with Bib and Tib (Bib = 1,3-bis(4,5-dihydro-1H-imidazol-2-yl)benzene; Tib = 1,3,5-tris(4,5-dihydro-1H-imidazol-2-yl)benzene) and were structurally and magnetically characterized. X-Ray single-crystal diffraction showed that each Co(II) ion was in a highly distorted tetrahedral coordination geometry with a cis-trans ratio of 1 : 2 from the Bib ligand, which functioned in a bidentate fashion in the binuclear triple-helical [Co2(Bib)3Cl2]2+ cations in 1 and 2. In the [Co3K1(Tib)2(CH3COO)6]- anions in 3, each Co(II) ion was also in a highly distorted tetrahedral coordination geometry and the Tib ligands acted in an offset fashion in C, C, C and A, A, A coordination to the Co(II) ions with pi-pi stacking interactions between two benzene rings from the Tib ligand in the cluster cation. Each Tib ligand in a cluster unit acted as a tridentate entity to coordinate three Co(II) ions resulting in a cylinder-like cluster structure. The intermolecular hydrogen bonds in the solid-state resulted in the well-shaped 2D layer network which formed a honeycomb in 1, the 3D supramolecular architecture which was connected to the 2D sheet into 3D in 2 and the 3D supramolecular architecture, which was extended into a well-shaped 2D honeycomb layer network in 3. The results from magnetic data, in the high-temperature region, showed that 1 and 2 obeyed the Curie-Weiss law with a Weiss constants theta = -12.3, and -9.8 K and a Curie constants C = 5.31 and 5.32 cm3 K mo1(-1), respectively, indicating antiferromagnetic interactions between adjacent cobalt(II) ions. Both complex 1 and 2 showed magnetic ordering at low temperature due to the canting effect. The zero-field AC magnetic susceptibility measurements for 1 and 2 displayed a maximum which was frequency dependent owing to a slow relaxation process, which could be caused by either domain wall movements or spin-glass behaviours.

Syntheses, crystal structures and anion-exchange properties of novel coordination polymers with imidazole-containing tripodal ligands

Six novel coordination polymers, [Cu(tib) 2(N 3) 2] · 2H 2O ( 1), [Cd(tib) 2(H 2O) 2](NO 3) 2 ( 2), [Cu(dien)(tib)](ClO 4) 2 · tib · CH 3CN ( 3), [Mn(ibimb) 2(H 2O) 2]Cl 2 · 2H 2O ( 4), [Zn(titmb) 2](NO 3) 2 · 2MeOH ( 5) and [Cd 3(titmb) 2Br 6] ( 6), where tib = 1,3,5-tris(1-imidazolyl)benzene, dien = diethylenetriamine, ibimb = 1-(1-imidazolyl)-3,5-bis(imidazol-1-ylmethyl)benzene, titmb = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, were obtained by self-assembly of tripodal ligands with the corresponding metal salts, and their structures were determined by single crystal X-ray diffraction analyses. Complexes 1 and 2 have similar 2D network structure in which only two of three imidazole groups of each tib ligand coordinated to the metal atoms and the additional one did not participate in the coordination. Complex 3 has a 1D chain structure in which there are two kinds of tib ligands, one kind of tib serves as a two-connecting (bridging) ligand using its two arms. The other kind of tib acts as guest molecule filled in the void of cationic 1D chains. Complex 4 has an infinite 1D hinged chain structure and ligand ibimb serves as a two-connecting (bridging) ligand using its two flexible arms. Complex 5 has a 2D honeycomb network structure with (6,3) topology in which titmb acts as a three-connecting ligand. Complex 6 has an infinite 1D chain structure in which each titmb ligand connects three metal atoms. Ligand titmb has cis, trans, trans-conformation in 6, which is different from that in complex 5( cis, cis, cis). The anion-exchange properties of complex 5 were investigated.