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In this work, four different bis(imidazole) ligands, namely 1,4-bis(1-imidazolyl)benzene (bib), 4,4′-bis(1-imidazolyl)biphenyl (bibp), 1,4-bis (imidazol-1-ylmethylene)benzene) (bimb) and 4,4′-bis(imidazol-1-yl)diphenyl ether (bidpe), were used as the second ligand to give rise to the structural diversity of a coordination polymer based on the cobalt-miipa (H2miipa = 5-(2-methylimidazol-1-yl) isophthalic acid) system. In compound 1, miipa2− coordinates to Co(II) atoms to form the Co-miipa 3D network. On introducing linear bis(imidazole) ligands with different lengths and rigidities into the Co(II)-miipa system, the obtained compounds 2–4 form similar three-fold interpenetrating 3D MOFs constructed from the Co(II)-miipa layers pillared by bis(imidazole) ligands. While introducing the V-shaped half-flexible bis(imidazole) ligands, the obtained compound 5 exhibits a 2D double-layered network built from the Co(II)-miipa 1D quadrangular prism linked by the bis(imidazole) ligand. Each 2D double layer is further interlocked with two neighboring ones to produce an interesting 3D framework. Significantly, CoNC-5 derived from a mixture of dicyandiamide (DCD) and compound 5 with a low void volume shows a superior electrocatalytic performance for the oxygen reduction reaction. The Eonset (0.974 V) and E1/2 (0.830 V) of CoNC-5 in O2-saturated 0.1 M KOH at 1600 rpm and 5 mV s−1 are superior to those of Pt/C (0.968 and 0.799 V). The JL value of CoNC-5 (JL = 5.29 mA cm−2) is higher than that of Pt/C (5.09 mA cm−2). [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu 3 (CN) 3 (tib)] n ( 1 ), [Cu 4 (CN) 4 (tib)] n ( 2 ), and [Cu 2 (CN) 2 (tib)] n ( 3 ), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ 2 -cyanides and a μ 3 -cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 Å). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250–350 °C. Complexes 1 – 3 show similar orange emission band at 602 nm originating from LMCT mechanism. [ABSTRACT FROM AUTHOR]

Metal salts and 3/4-pyridyltetrazoles (3/4-Hptz) react with oxalic acid (H2ox), 1,2,4,5-benzenetetracarboxylic acid (H4btec), isophthalic acid (H2ip), and 1,2,3,4-butanetetracarboxylic acid (H4btca) to afford six coordination polymers, namely, [Cu(4-ptz)(ox)0.5]n (1), [Cu(4-Hptz)(btec)0.5]n (2), [Co2(3-ptz)(ip)(OH)(H2O)]n (3), {[Co1.5(3-ptz)(btca)0.5(H2O)]·H2O}n (4), {[Co3(4-ptz)2(btca)(H2O)3]·2H2O}n (5), and {[Cd2(4-ptz)2(btca)0.5(H2O)3]·DMF·4H2O}n (6). Their structures were characterized by EA, IR, PXRD, TGA, and single-crystal XRD. 3/4-Pyridyltetrazoles display μ2-, μ3-, and μ5-coordination modes in them. Complex 1 is a 3D MOF constructed from a 2D (4,4) [Cu(4-ptz)]n grid pillared by an oxalate spacer. Complex 2 displays a 2D network containing a square planar Cu1 and elongated octahedral Cu2 centers. Complex 3 shows a 2D network containing μ5-ptz, μ3-ip, and μ3-OH. Complex 4 exhibits a 3D MOF assembled by a 2D [Co1.5(btca)0.5]n network pillared by a 3-ptz spacer. Complex 5 displays a 3D porous MOF with nanosized rectangular tunnels. Complex 6 features a 3D porous MOF built by 2D [Cd2(4-ptz)(btca)0.5]n network pillared by a 4-ptz spacer. Variable-temperature magnetic susceptibility and magneto-structural correlation studies indicate that five CuII/CoII complexes present remarkable magnetic coupling diversity from ferro-, to ferri-, to antiferromagnetic interactions. Complex 1 shows strong antiferromagnetic behavior originating from the oxalate-bridging CuII dimer (Jox = −94.7 cm-1) and the tetrazole-bridging CuII dimer (Jptz = −61.0 cm-1). Complex 2 presents a weak ferromagnetic interaction (J = 0.82 cm-1) originating from the magnetic orbital orthogonality between square planar CuII and octahedral CuII centers. Complex 3 displays ferrimagnetic coupling in the Co3(μ3-OH) triangle. Two btca CoII complexes show antiferromagnetic interactions originating from carboxyl-bridging trinuclear CoII clusters with the θ values of −17.08 K for 4 and −8.6 K for 5. The thermal behaviors of these nitrogen-rich tetrazole complexes are investigated. Anhydrous complexes 1-3 containing rigid polycarboxylates are thermally stable to 250-300 °C and then decompose explosively, whereas complexes 4-6 with flexible butanetetracarboxylate decompose smoothly. [ABSTRACT FROM AUTHOR]

MnII and CoII salts reacting with 4-(4-carboxyphenyl)-4,2′:6′,4″-terpyridine (4-Hcptpy) in DMF/H2O afford two complexes, [Mn(4-cptpy)(DMF)(H2O)2] n ·n(4-cptpy)·nDMF (1) and [Co(4-cptpy)2(H2O)2] n (2). Complex 1 is a 1D ribbon coordination polymer assembled by Mn2 dimer and tridentate 4-cptpy ligand. The guest 4-cptpy anion is embedded in 3D supramolecular architecture with strong hydrogen bonds. Complex 2 is a 1D linear chain coordination polymer with quadrangled pores. The complex 1 releases H2O and DMF in 87–150°C, and the anhydrous [Mn(4-cptpy)] n ·n(4-cptpy) remains thermally stable until 403°C. Variable temperature magnetic susceptibility study in 2–300K proves that a weak antiferromagnetic interaction exists in the (μ-O2CR)2Mn2 core. [ABSTRACT FROM AUTHOR]

A 2D tri-layer compound {[Co8(tbip)6(H2O)9(OH)4]·12(H2O)}n(1) (H2tbip = 5-tert-butyl isophthalic acid) consisting of novel heptacobaltate clusters and single cobalt centers bridged by tbip2−ligands has been hydrothermally synthesized. The complex represents a rare example of a homometallic coordination polymer built up from both heptanuclear metal clusters and single metal centers simultaneously. The magnetic investigation reveals that the complex exhibits the overall predominance of antiferromagnetic coupling between magnetic centers. [ABSTRACT FROM AUTHOR]

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 butca4- coordinates to four Cu(II) ions through four monodentate carboxylates. Complex 2 is a 1-D chain with tridentate H2butca2- coordinating to two Zn(II) ions through monodentate and chelating carboxylates. Complex 3 is a 1-D double-chain coordination polymer. H2chhca4- 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. [ABSTRACT FROM AUTHOR]

Abstract: Four novel coordination polymers constructed from flexible pamoic acid, namely [Co(pam)(4,4′-bipy)] n ·nH2O (1), [Ni(pam)(4,4′-bipy)(H2O)2] n ·2nCH3CN (2), [Cd(pam)(py)2] n ·npy (3) and [Mn2(pam)2(py)6(H2O)2] n ·2npy (4), (H2pam=pamoic acid, 4,4′-bipy=4,4′-bipyridine, py=pyridine), have been synthesized and characterized by elemental analysis, infrared spectra and X-ray crystallography. Complex 1 is a 2-D coordination polymer constructed from chelating bis-bidentate pam and 4,4′-bipyridine bridging ligands. Complex 2 is a 2-D coordination polymer assembled by bis-monodentate pam and 4,4′-bipyridine, where acetonitrile is filled in the rectangle channels. Both 2-D coordination polymers display undulated (4,4) grid layers as sql topology. Complex 3 displays a 1-D polymeric chain using chelating bis-bidentate pam as bridging ligand. Complex 4 exhibits an interesting bis-monodentate pam-Mn(II) 1-D polymeric chain, in which exist two-type six-coordinated manganese centers. Mn(1) is bound to four pyridine ligands, whereas Mn(2) is combined to two pyridine and two H2O molecules. Their thermal stabilities have been investigated. Cadmium complex 3 displays strong green luminescence with emission maximum at 543nm. [Copyright &y& Elsevier]

Hydrothermal reactions of AgNO 3 , K 3 [Fe(CN) 6 ] with N-heterocyclic ligands afforded three novel Ag(I)–cyanide coordination polymers, [Ag 2 (CN) 2 (tpt)] n ( 1 ), {[Ag(CN)(bpe) 0.5 ][Ag(CN)]} n ( 2 ) and [Ag(CN)(btmb) 0.5 ] n ( 3 ) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine, bpe = 1,2-bis(4-pyridyl)ethane, btmb = 1,2-bis(1,2,4-triazol-1-ylmethyl)benzene). In complex 1 , two Ag(CN) linear chains are bridged by bidentate tpt ligand to form a ladder-like structure, which are further connected by Ag Ag metal bond to generate a 2D polymeric network. Complex 2 is an interesting 3D supramolecular architecture assembled by 2D [Ag 1 (CN)(bpe) 0.5 ] n network and linear [Ag 2 (CN)] n chain combined by strong Ag Ag metal bond. Complex 3 is a 1D ladder-like double-chain polymer constructed from Ag–cyanide linear chains and btmb spacer, which is further extended to a 2D supramolecular network by Ag–Ag weak interaction. The Ag–Ag metal interactions play important roles in the construction of three coordination polymers. Complexes 1 and 2 are respectively thermally stable at 300 and 180 °C. Complexes 1 and 3 emit strong blue luminescence. [ABSTRACT FROM AUTHOR]

The article focuses on the growing interest in the synthesis and design of metal-organic coordination polymers. It discusses the intriguing molecular topologies and the structural diversity of metal-organic coordination polymers as well as their potential as a new class of solid-state materials. It also highlights the important role played by the judicious selection of bridging ligands in the construction of such materials.

Abstract: Two new three-dimensional (3D) coordination polymer [Cu2(tetrazolate)3(OH)] n (1) and [Cd2(tetrazolate)3Br] n (2) were synthesized and structurally characterized. By the topology analysis, the complicated architecture of 1 and 2 are all simplified to be the 6-connected pcu-type net. The variable-temperature magnetic susceptibilities (5–300K) of 1 shows antiferromagnetic interactions of copper(II) ions bridged tetrazolate ligands and/or hydroxide anion. [Copyright &y& Elsevier]

[Display omitted] • Six 5,5′-(1,2-phenylenebis(methoxy))diisophthalate coordination polymers were prepared. • The tetracarboxylic acid displays seven types of coordination modes. • These complexes exhibit 2D networks and 3D porous MOFs. • Mn(II) complexes 1 and 2 have antiferromagnetic couplings. Mn(II)/Cd(II) nitrates react with 5,5′-(1,2-phenylenebis(methoxy))diisophthalic acid (H 4 L) and four dipyridyl-typed N -donor ligands to afford six coordination polymers, {[Mn 2 (L)(bpee) 2 ]·DMF} n (1), {[Mn 3 (H 2 L) 3 (bpmp)(H 2 O) 2 ]·2DMF·2H 2 O} n (2), {[(CH 3) 2 NH 2 ] 2 [Cd(L)]·2H 2 O} n (3), [Cd 2 (L)(H 2 O) 2 (DMF)] n (4), {[Cd(L) 0.5 (bpdb)]·DMF} n (5) and [Cd(H 2 L)(bpp)(H 2 O)] n (6) [bpee = 1,2-bis(4-pyridyl)ethylene, bpmp = 1,4-bis(4-pyridylmethyl)piperazine, bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, bpp = 1,3-bis(4-pyridyl)propane]. These complexes were characterized by elemental analyses, IR spectra, PXRD, thermogravimetry and X-ray structural analysis. H 4 L displays seven types of coordination modes in them. Four complexes are 3D coordination polymers, except 2D wave-like network of complex 3 and 1D double-chain polymer of complex 6. Cd(II) complexes 3 , 4 and 6 display strong blue luminescence. Complex 1 exhibits weak antiferromagnetic coupling in [Mn 2 (μ 2 -COO) 2 (COO) 2 ] dimer, while complex 2 shows antiferromagnetic coupling in [Mn 3 (μ 2 -COO) 6 ] trinuclear cluster. [ABSTRACT FROM AUTHOR]

Seven novel coordination polymers based on 2,2′-phosphinico-dibenzoic acid (H3L), namely, {[Zn3L2(H2O)4]·2H2O}n (1), [Zn3L2(4,4′-bipy)2]n (2), [Zn(HL)(2,2′-bipy)(H2O)]n (3), {[Cd9L6(H2O)8]·4H2O}n (4), [Cd8L4(OH)2(OAc)2(4,4′-bipy)]n (5), [Mn3L2(4,4′-bipy)(EtOH)(H2O)2]n (6), and [Mn(HL)(2,2′-bipy)(H2O)]n (7), were synthesized under hydro(solvo)thermal conditions. These compounds crystallize in the triclinic P1̅ space group for 1, 4, 5, and 6, the monoclinic space group C2/c for 2, and the monoclinic P21/c space group for 3 and 7. The L3- ligand displays versatile binding modes in 1-7. Compound 1 is a one-dimensional (1-D) chain coordination polymer with a three-dimensional (3-D) supramolecular framework. Compound 2 is a 3-D porous metal-organic framework (MOF) with two different 4,4′-bipyridine linkers. Compounds 3 and 7 show 1-D zigzag chain structures. Compound 4 exhibits a sophisticated 3-D MOF constructed from two types of Cd8 clusters and one Cd2 dimer, which is the first example exhibiting the coexistence of four coordination modes of L3- ligands and four geometries of Cd(II) ions in one network. Compound 5 displays a two-dimensional (2-D) network containing a ring-like Cd8 cluster. Compound 6 shows a 2-D layered network with 4,4′-bipyridine linker. Their luminescence and variable-temperature magnetic property were investigated, which indicated ligand-centered emission in 1-5 and weak antiferromagnetic coupling between Mn(II) ions in 6 and 7. [ABSTRACT FROM AUTHOR]

Highlights: [•] Three camphorate coordination polymers were prepared. [•] Complex 1 is a chiral 1D helical chain polymer and 2 exhibits a chiral 2D network. [•] Complex 3 is an achiral 2D polymer in which partial d-camphorate changes to l-camphorate. [•] Complexes 1 and 2 show violet luminescence, 3 exhibits an antiferromagnetic interaction. [ABSTRACT FROM AUTHOR]

Abstract: Reactions of different metal salts with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) gave rise to five new complexes, namely [Cu4(CN)4(3-abpt)2] n (1), [CuBr(3-abpt)] n (2), [CuI(3-abpt)] n (3), [Cu3I3(3-abpt)] n (4) and [Cu(3-abpt)(SO4)(H2O)] n (5). Compounds 1, 3, 4 and 5 are all 2D structures. Compound 1 is a double-layered polymer with an uncommon 3-nodal 3-connected (103)(102.4)4 network, 3 shows a 2D square layered structure, 4 is also a double-layered polymer with 2-nodal 4-connected (3.4.5.62.7)2(3.42.52.7) network and 5 is a 2D structure which is ultimately stacked with an ABAB repeat pattern. Compound 2 is a 1D coordination polymer which exhibits a ladder-like network. The photoluminescence of 1–2 has also been investigated. The long emission lifetimes of 1–2 could be assigned to metal-to-ligand charge transfer triple excited states [MLCT]. [Copyright &y& Elsevier]

The hydrothermal/solvothermal reactions of metal(II) nitrate hydrates with organic ligands (p-benzenediacrylic acid = H2pbda, 1,10-phenanthroline = phen) generate three three-dimensional (3-D) coordination polymers with (3,4)-connected (4.8.10)(42.6.8 × 102) topology (1, {[Cd2(pbda)2(phen)2](H2O)}n), 2-fold interpenetrating CdSO4-type open framework (2, [Zn3(pbda)3(phen)2]n), and 3-fold interpenetrated sra net (3, [Pb(pbda)]n). The porous zinc open framework 2 has the typical type-I sorption curve with a H2 uptake of 31 cm3·g−1(STP) at 77 K, BET surface area of 65.84 m2·g−1, and meso-[Zn2(pbda)2] helical motifs. With strong luminescent emission at 504 nm, complex 2 may be suitable as an excellent candidate for solid-state photosensitive materials at room temperature. Three-dimensional {[Cd2(pbda)2(phen)2](H2O)}n (1), [Zn3(pbda)3(phen)2]n (2), and [Pb(pbda)]n (3) are reported (H2pbda = p-benzenediacrylic acid, phen = 1,10-phenanthroline). Topologies of three metal(II)-organic coordination polymers are investigated. Complex 2 has the typical type-I sorption curve with a H2 uptake of 31 cm3·g−1(STP) at 77 K and luminescent emission at 504 nm at room temperature. [ABSTRACT FROM AUTHOR]

Abstract: Two novel three-dimensional (3D) coordination polymers (1) and ·nH2O (2) (mtta=5-methyltetrazolate, trz=1,2,4-triazole) were synthesized and structurally characterized. Complex 1 shows a 3D porous metal–organic framework. By the topology analysis, the complicated architecture of 1 can be simplified to be the 4-connected diamond-type net. Compound 2 is a two-fold interpenetrating 3,5-connected 3D framework with new topology. [Copyright &y& Elsevier]

Abstract: Reactions of metal acetates with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) and co-ligands gave rise to four new complexes, namely [Zn2(3-abpt)(beta)(DMF) (H2O)2] n ·nH2O (1), [Zn(3-abpt)(ip)] n ·3nH2O (2), [Zn(3-abpt)(ip)(H2O)2] n ·2nH2O (3), and [Cu2(3-abpt)2(C6H5COO)4(H2O)2] n ·2nH2O (4) (ip=isophthalate, beta=1,2,4,5-benzenetetracarboxylate). Compound 1 is a 3D coordination polymer with uncommon 3,4-connected (62.8)2(62.82.102) network. Compounds 2–4 are all 1D coordination polymers, which exhibit diversity structures. Compound 2 is a tubular-like chain, 3 is a ring-like network, and 4 is a zigzag chain. Their thermal stabilities and the photoluminescence of 1 have also been investigated. [Copyright &y& Elsevier]

Abstract: Reactions of 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) with metal acetates gave rise to four new complexes [Cu(3-abpt)(ip)] n ·2nH2O (1), [Co(3-abpt)(ip)(H2O)2] n ·2nH2O (2), [Ni(3-abpt)(tp)(H2O)2] n (3) and [Cu(3-abpt)2(CH3COO)2(H2O)2] (4) (ip=isophthalate, tp=terephthalate), which were characterized by EA, IR and X-ray crystallography. Compound 1 consists of two kinds of ring-like chain which are interconnected to form an unusual two-dimensional layered motif. Compounds 2 and 3 are both 1D ring-like infinite chains. Compound 4 is a mononuclear complex. The thermal stabilities of coordination polymers 1–3 have been investigated. [Copyright &y& Elsevier]

Four cadmium complexes with flexible polycarboxylic acid ligands have been synthesized. The bidentate auxiliary ligands with different lengths and flexibility play an important role to affect their final structures. The luminescent sensing of compounds 1 and 4 toward nitrobenzene has also been investigated. • Four cadmium coordination polymers have been synthesized by using flexibly carboxylic ligand. • The auxiliary ligands play an important role to affect their final structures. • Compound 1 and 4 might be developed as a functional luminescent probe for detecting nitrobenzene. Reactions of cadmium ions with the flexible tetracarboxylic ligand, 5-(bis(4-carboxybenzyl)amino) isophthalic acid (H 4 L) gave rise to four complexes, namely {[(Me 2 NH 2) 2 Cd 3 (L) 2 ]∙10H 2 O)} n (1), {[Cd 2 (L)(pdp)(H 2 O) 2 ]∙2DMF·4H 2 O} n (pdp = 4-[(E)-4-Pyridinylazo]pyridine) (2), {[Cd 2 (L)(bpe)(H 2 O) 2 ]∙2DMF·4H 2 O} n (bpe = 1,2-bi(4-pyridyl)ethene) (3) and {[Cd 4 (L) 2 (bpmp) 3 ]∙2H 2 O} n (bpmp = N,Nʹ -bis-(4-pyridyl-methyl) piperazine) (4). Compound 1 features a three-dimensional anionic architecture constructed by triangular Cd 3 cluster and ligands, with rectangle channels encapsulating [Me 2 NH 2 ]+ cations. Compounds 2 and 3 present similar structures, exhibiting the 2D polythreading layer. Compound 4 possesses a 3D structure with 4,6-connected new topology. The powder X-ray diffraction, the thermal stabilities, and solid-state luminescence properties were studied for 1 – 4. Furthermore, the luminescent sensing of compounds 1 and 4 toward nitrobenzene has also been investigated. [ABSTRACT FROM AUTHOR]