•A novel 2D CdIIcoordination polymer with highly stable in water was synthesized based on N-containing pyrazol group dicarboxyl rigid ligand.•The compound performed excellent luminescence for good selectivity and high sensitivity to Fe3 + and 2,4,6-trinitrophenol with fluorescence quenching mechanism.The assembly of a N-containing heterocyclic dicarboxyl rigid ligand with a cadmium ion resulted in the formation of a 2D coordination polymer {[Cd(PYIA)(H2O)]·H2O}n (H2PYIA = 5-(2H-Pyrazol-3-yl)-isophthalic acid) (SUF-1). The compound SUF-1 determined by single crystal X-ray diffraction showed a 2D double layer plane structure containing a six-coordinated Cd2 + bimetallic cluster. SUF-1 was highly stable and strongly emitted blue light in water at ambient temperature. Significantly, it exhibited excellent selectivity and highly sensitivity detective of Fe3 + and 2,4,6-trinitrophenol with a fluorescence quenching mechanism in water.A new 2D double layer coordination polymer {[Cd(PYIA)(H2O)]·H2O}n (SUF-1) was synthesized based on a rigid N-containing ligand, which exhibited excellent selectivity and highly sensitivity detective of Fe3 + and 2,4,6-trinitrophenol with a fluorescence quenching mechanism in water.Download high-res image (110KB)Download full-size image

Four temperature-dependent KI-induced KI–LnIII heterometallic coordination polymers, {[LnK(OBA)2(μ2-OH2)]·4H2O}n (Ln = Tb(1), Dy(2), H2OBA = 4,4′-oxybisbenzoic acid) and {[Ln3K(OBA)4(μ2-HCOO)(μ3-HCOO)2]·2H2O}n (Ln = Tb(3), Dy(4)), have been synthesized under hydrothermal conditions by controlling the temperature. Notably, compounds 1 and 2, consisting of an unique nine-nuclear cluster secondary building unit (SBU), [Ln4K5(–CO2)16(μ2-H2O)4], linked to each other by OBA2−, can be simplified as a highly 12-connected three-dimensional (3D) network with fcu topology. Comparably, compounds 3 and 4 consist of a rare four-nuclear cluster SBU, [Ln3K(–CO2)6(μ2-HCOO)2(μ3-HCOO)4], which are linked to each other by OBA2− resulting in a highly 10-connected tcg topology. The luminescent properties of 1 and 3 were studied and the solid-state magnetic measurements reveal antiferromagnetic behaviors of 2 and 4.

•Two novel cyclohexane-like metallamacrocycles were synthesized.•An unprecedented self-assembly strategy of six-membered metallacrocycles has been presented.•The unusual structure of 1and 2 were investigated.Two novel cyclohexane-like metallamacrocycles [ZnCH3COO(L)]6·solvent (1) and [Zn(HNO3)(L)]6·solvent (2) (HL = 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine) have been synthesized under hydrothermal conditions and characterized by IR spectra, single crystal X-ray diffraction, PXRD analysis, thermogravimetric analysis. The X-ray single crystal diffraction indicates that the self-assembly of the metallamacrocycle generates a fused-ring network that is further assembled into a 3D structure with 1D suprachannels. In particular, a designed self-assembly strategy has been applied to achieving six-membered Zn–organic metallamacrocycles unprecedentedly.3D supramolecular frameworks with 1D suprachannels generated by self-assembly based on supramolecular interactions of Zn–organic cyclohexane-like metallamacrocycles.

•Three Cd(II) coordination polymers were synthesized.•Auxiliary organic compounds and temperature play a significant role in constructing CPs.•The luminescent properties of 1–3 was investigated in solid state.Three interesting metal-organic frameworks, [(Cd2(Hpidc)(pdc)]n(1), {[(Cd2(Hpidc)2(H2O)]·H2O}n(2), {[(Cd2(Hpidc)2(H2O)]·2H2O}n(3) (H3pidc = pyridine-2-yl-1H-imidazole-4,5-dicarboxylic acid, H2pdc = 2,6-pyridine dicarboxylic acid) have been synthesized under hydrothermal by controlling the temperature and varying with the second organic ligands. Compounds 1 and 2 possess 3D frameworks with a new topological network with 2-nodal (6, 6)-connected net and 2-nodal (5, 6)-connected net respectively. Notably, Compound 3 exhibit a 1-D interesting double Zigzag chain. The thermogravimetric and fluorescence properties of 1–3 were also explored.Six coordinate compounds obtained with various auxiliary ligands.

A series of lanthanide microporous coordination polymers, namely, {[Ln4(OBA)6(DMF)(H2O)]·2DMF·3H2O}n [Ln = Nd(1), Sm(2), Eu(3), Gd(4)]; {[Ln4(OBA)6(H2O)2]·3DMF·2H2O}n [Ln = Tb(5), Dy(6)]; {[Ln4(OBA)6(DMF)(H2O)2]·2DMF·4H2O}n [Ln = Tb(7), Dy(8)] (H2OBA = 4,4′-oxybisbenzoic acid, DMF = N,N′-dimethylformamide), have been successfully prepared via solvothermal methods and characterized by FT-IR, photoluminescence spectra, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. All of the lanthanide coordination polymers showed three dimensional (3D) metal–organic frameworks. The structural variations in compounds 1–8 may be caused by lanthanide contraction and different coordination modes of V-shaped H2OBA ligands. The luminescence properties of compounds 3, 5 and 7 have been studied in the solid state at room temperature, and all of them displayed metal-based luminescence. Moreover, compounds 4, 6 and 8 exhibited antiferromagnetic coupling within the carboxyl oxygen bridged rare-earth chains.

•An 3D monometallic complex and the first heterometallic examples based on 2,6-dimethylpyridine-3,5-dicarboxylic acid have been synthesized.•Two kinds of 3D frameworks feature 5, 6-connected and 3, 4, 5, 6-connected topology, respectively.•Complexes 1, 3, 5 exhibit characteristic lanthanide-centered luminescence, while compounds 4 and 6 show antiferromagnetic behaviors.Two kinds of three-dimensional (3D) coordination frameworks from monometallic to heterometallic, including a charming 3D monometallic complex, namely, [Eu2(mpda)3(H2O)4]n (1) and the first series of novel 3D heterometallic 4d–4f coordination frameworks based on 2,6-dimethylpyridine-3,5-dicarboxylic acid, namely, [Ln2Cd2(mpda)2(bdc)2(SO4)2(H2O)6]n [Ln = Sm(2), Eu(3), Gd(4), Tb(5), Dy(6); mpda = 2,6-dimethylpyridine-3,5-dicarboxylic acid; bdc = 1,4-benzenedicarboxylic acid] have been successfully synthesized under hydrothermal conditions and structurally characterized. Crystal 1 is featured by its interesting 3D chain-layer construction which is formed by the alternative arrangement of chains and layers and exhibits 2-nodal 5, 6-connected 3D network with the Schlafli symbol of {33.43.55.64}{36.46.53}. Complexes 2–6 are isostructural and it reveals that these 3D heterometallic compounds are firstly built by H2mpda ligand. What is worth mentioning is that anionic ligand SO42 − plays a crucial function in the construction building. The two-dimensional (2D) lanthanide-transition heterometallic bilayers [Ln2Cd2(mpda)2(bdc)2]n are pillared by SO42 − subunits forming mixed-ligand complexes with a pillared-layer 3D structure. Complexes 2–6 feature 4-nodal 3, 4, 5, 6-connected 3D frameworks with {4.82}{4.84.10}{42.810.102.12}{42.88} topology. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 1, 3, and 5 and the magnetic properties of complexes 4 and 6 were also investigated in detail.Two kinds of 3D coordination frameworks, containing an interesting 3D monometallic complex and the first series examples of Ln(III)–Cd(II) 4d–4f 3D heterometallic compounds, have been successfully synthesized under hydrothermal conditions based on 2,6-dimethylpyridine-3,5-dicarboxylic acid.

•Four 1D–3D Ln(III) organodisulfonate coordination polymers have been synthesized.•They are the further research of coordination between nds, phen and rare earth Eu.•The luminescent property of compound 1 was investigated in solid state.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.Compounds 1, 2, 3 and 4 exhibit different 1D to 3D structures owing to different stoichiometric ratio of the reactants.

The hydrothermal reaction of rare earth nitrates, CuCN, 1H-1,2,3-triazole-4,5-dicarboxylic acid (H3tda), and isonicotinic acid (Hina) resulted in the formation of a new series of 3d–4f heterometallic coordination polymers [LnCu(tda)(ina)2(H2O)]·3H2O (Ln = Eu (1), Tb (2), Gd (3), Dy (4), Ho (5)], H3tda = 1H-1,2,3-triazole-4,5-dicarboxylic acid, Hina = isonicotinic acid). Complexes 1–5 are isostructural and structurally characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis (TGA), and single-crystal powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis reveals that the metal cations in these compounds are firstly interconnected by H3tda ligands to produce a carpet-shaped heterometallic ring [Ln2(tda)2Cu4], and then pillared by bridging Hina molecules to form the 3D layer-pillared porous Ln(III)–Cu(II) heterometallic coordination polymers. In addition, the magnetic properties of 1–5 were also investigated in detail.

To explore the influence of different carboxylate ligands on the structures of metal–organic frameworks (MOFs), five novel Zn(II) coordination polymer compounds, namely, {[Zn(atz)(bia)]}n (1), {[Zn3(atz)3(tpa)3/2]}n (2), {[Zn2(atz)2(pda)]}n (3), {[Zn4(atz)2(btc)]·4H2O}n (4) and {[Zn2(atz)2(btec)]·H2O}n (5) have been successfully obtained by introducing various secondary auxiliary ligands in Zn(II)–L systems, characterized by elemental analysis, FT-IR, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction (Hatz = 3-amino-1,2,4-triazolate, Hbia = benzoic acid, H2tpa = 1,4-terephthalic acid, H2pda = 1,4-benzenediacetic acid, H3btc = 1,3,5-benzenetricarboxylate, H4btec = 1,2,4,5-benzenetetracarboxylic). Compound 1 features a 2D layer with (4.82) topology, which is further stabilized by hydrogen bonds between the uncoordinated amino groups and uncoordinated oxygen atoms from bia ligands. Compound 2 exhibits a 3D 3,4-connected framework with {4.82.103}{4.82} topology, constructed from Zn(II) ions and μ3-atz ligand. Compound 3 displays a 3D 3,4-connected network with {4.6.8}{4.62.83} topology. Compound 4 possesses a 3D 9-nodal network with a point symbol of {4.8.9}2{4.82}{4.83.9.10}{5.8.9}4{5.82}. Compound 5 shows a 3D 3,4,4-connected framework with {4.82}4{42.83.10}2{84.102} topology. The diverse structures of these five complexes demonstrate that the skeleton of carboxylate ligands have a significant impact on the construction of MOFs. Moreover, the luminescence properties of complexes 1–5 were investigated in the solid state.

Four novel functional supramolecular metal–organic coordination polymers, [Cd2Cl3(IP)2(NIPH)2](1), [Zn2(IP)2(μ2-SO4)2(NIPH)2]·2H2O(2), [Cd(IP)2(BPDC)](3), [Zn2(IP)2(NDC)2](4) (IP = 1-H-imidazo[4,5-f][1,10]-phenanthroline, H2NIPH = 5-nitro-isophthalic acid, H2BPDC = 4,4′-biphenyldicarboxylic acid, H2NDC = 2,6-naphthalenedicarboxylic acid), have been obtained through three types of dicarboxylate linkers. All the four compounds are extended into a 3-D supramolecular framework by hydrogen bonds or weak aromatic interactions. The different structures demonstrate the effect of the dicarboxylate ligands on the formation of such coordination architectures. Compound 1 is a 1-D double-stranded loop-like chain with repeated [Cd4(Cl)4]4 + units connected by H2NIPH ligands. In compound 2, there are two indie 1D zigzag chains jointed by sulfate anions with μ2-bridging mode. With different metal centers, compounds 1 and 2 hold different crystal structures. With different auxiliary dicarboxylate ligands, compounds 3 and 4 exhibit disparate 1D chains. The fluorescence property and thermal stability of all complexes are also investigated.The synthetic route of complexes 1–4.Highlights► All compounds exhibit 3D supramolecular net with intermolecular weak interactions. ► With different metal centers, compounds 1 and 2 possess different crystal structures; ► With different auxiliary ligands, compounds 3 and 4 exhibit disparate 1D chains.

Two different types of novel lanthanide coordination polymers constructed from 5-nitroisophthalic acid, and picolinic acid as auxiliary ligand, namely, {[Ln2(nip)2(pic)2(H2O)]}n (type I, Ln = Pr 1, Nd 2, Sm 3, Eu 4, and H2nip = 5-nitroisophthalic acid, Hpic = picolinic acid), and {[Ln4(nip)5(pic)2(H2O)2]·2H2O}n (type II, Ln = Tb 5, Dy 6, Ho 7, Er 8), have been hydrothermally synthesized and characterized by IR, elemental analysis, thermogravimetric analysis (TGA), single-crystal X-ray diffraction analyses and powder X-ray diffraction (PXRD). Complexes 1–4 (type I) are isostructural and the infinite 1D Sm-carboxylate chains are bridged by pia ligands to form 2D sheets, such sheets are further united together to generate a 3D supramolecular structure. Complexes 5–8 (type II) are isostructural and the infinite 1D Tb–carboxylate chains are bridged by pia ligands to form 2D sheets, such sheets are further united together to generate a 3D supramolecular structure. Furthermore, the luminescence properties of compounds 4 and 5 have also been studied.The coordination modes of H2nip and Hpic ligands.Highlights► Two different types of novel lanthanide coordination polymers have been synthesized. ► Lanthanide contraction affects the structure of eight complexes. ► Complexes 4 and 5 exhibit characteristic lanthanide-centered luminescence.

•Three 3D Ln(III)-Zn(II) 3d-4f heterometallic coordination polymers (HCPs) have been synthesized.•Complexes 1 and 3 exhibit characteristic lanthanide-centered luminescence.Three 3D Ln(III)–Zn(II) 3d-4f heterometallic coordination polymers (HCPs) constructed from the coligands 3-amino-1H-1,2,4-triazole and oxalate, {[Ln2Zn19(atz)18(ox)9(Cl)8]·17H2O}n(Ln = Eu 1, Gd 2, Tb 3, Hatz = 3-amino-1H-1,2,4-triazole, ox = oxalic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, FT-IR, TG analysis and X-ray diffraction. X-ray diffraction analysis reveals that these complexes are isostructural and feature 3D pillar-layered coordination frameworks constructed by the linkages of 2D layers and 1D zigzag chains, possessing a 5-nodal net topology with Schläfli symbol of {32;52;62}3{33;44;57;65;72}6{33;45;55;6;7}6{36;415;56;6}2{53}4. In addition, the magnetic property of 2 and the luminescence properties of 1 and 3 were also investigated.The neighboring 2D planars connected together into a 3D supramolecular architecture by Hatz ligand. All amino groups were omitted for clarity.

•A series of Ln(III)-Ag(I) 4d-4f heterometallic polymers have been synthesized.•They are the first 4d-4f heterometallic polymers built by 4,4’- oxybis (benzoicacid).•The luminescent property of polymer 1 was investigated in the solid-state.A series of Ln(III)-Ag(I) 4d–4f heterometallic coordination polymers [LnAg(oba)2(H2O)]n (Ln = Dy 1, Ho 2, Er 3) have been synthesized under hydrothermal reactions of 4,4′-oxybis(benzoicacid) (H2oba) with Ln(NO3)3 · 6H2O and AgNO3 at 180 °C. All complexes are isostructural with 3D networks expanded from 1D zigzag chains and 2D layers. In addition, the luminescent property of compound 1 was investigated in the solid-state at room temperature.The coordination mode of H2oba ligand.

Two series of lanthanide coordination polymers with formular [Ln(Haip)(ox)(H2O)] (type I) (Ln = Ce(1), Pr(2), Nd(3), Sm(4), Eu(5), Gd(6), Tb(7)) and [Ln2(aip)2(ox)(H2O)]·H2O (type II) (Ln = Dy(8), Ho(9), Er(10), Tm(11)) have been synthesized by hydrothermal reactions of 5-aminoisophthalic acid (H2aip) and oxalate (ox) with corresponding lanthanide nitrates or lanthanide oxides. Complexes 1–7 (type I) are isostructural and possess 6-connected 2D layer structure with Schläfli symbol (36;46;53). Complexes 8–11 (type II) are also isomorphous and feature 9-connected 3D framework with Schläfli symbol (312;416;57;6). The solid-state luminescent properties of 5 and 7 containing Eu3 + and Tb3 + were measured at room temperature. The magnetic properties show complexes 6 and 8 have antiferromagnetic behavior. Furthermore, infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA), powder X-ray diffraction (PXRD) of these complexes are also investigated.Graphical abstractThe synthetic route of complexes 1–11.Highlights► Eleven novel 2D/3D lanthanide coordination polymers have been synthesized. ► Lanthanide contraction affects the structure of the eleven complexes. ► 2D complexes show 6-connected topology and 3D complexes show 9-connected topology.

Six novel functional metal–organic frameworks, namely, [CdCl(IP)(Hpydc)(H2O)]·2H2O (1), [Cd(IP)(H2imdc)]Cl (2), [Cd(IP)2(H2O)2](1,5-nds)·2H2O (3), [Co(IP)(H2O)4](1,5-nds)·H2O (4), [Zn(IP)(μ2-SO4)(H2O)]·H2O (5), [Zn(IP)(SO4)(H2O)3] (6) (IP = 1-H-imidazo[4,5-f][1,10]-phenanthroline, H2pydc = pyridine-2,6-dicarboxylic acid, H3imdc = imidazole-4,5-dicarboxylic acid, 1,5-nds = 1,5-naphthanlenedisulfonate), were synthesized by controlling auxiliary ligands, metal centers and solvents. In compound 1, Cd(II) is chelated by IP and Hpydc ligands, forming 0D → 3D supramolecular structure. Compound 2 is a 1D chain with repeated [Cd(IP)]2+ units connected by H2imdc ligands. With different metal centers, compounds 3 and 4 possess different crystal structures. With solvents regulated, compounds 5 and 6 exhibit distinct structures. In compound 5, sulfate anions show μ2-bridging mode, which results in the formation of 1D chain. In compound 6, only one oxygen atom from sulfate anion coordinates to the metal center, resulting in discrete repeated units. The luminescent properties of 1, 2, 3, 5, 6 and thermal stabilities of all compounds were measured.Six compounds were synthesized by controlling extra ligands, metal centers and solvents.Highlights► Six novel supramolecular coordination polymers have been synthesized. ► Reaction conditions affect the structure of the six compounds. ► Five compounds exhibit luminescent properties.

Two new 3D 3d–4f heterometallic microporous metal-organic frameworks, named, [Ln2Ni(Himdc)2(aip)2(H2O)4]·6H2O [Ln = Nd (1), La (2); H3imdc = imidazole-4,5-dicarboxy acid; aip = 5-aminoisophthalic acid], have been successfully synthesized through the reaction of Ln2O3, NiSO4·6H2O, H3imdc, aip and H2O. Compounds 1 and 2 are isomorphic, displaying rare interesting 3D heterometallic networks with (7, 8)-connected topology based on the linkages of 2D layers and 1D zigzag chains. In addition, the magnetic properties of the two compounds have been investigated.The 2D layer structure based on 1D zigzag chains and Ni(II) centers, and further linked by the aip ligands to form interesting 3D microporous frameworks.Highlights► Two novel 3D heterometallic microporous complexes have been synthesized. ► The 3D heterometallic network with (7, 8)-connected topology. ► Both complexes exhibit antiferromagnetic behavior.

A novel mixed metal–organic framework, 2H3O·[NaCd3(C14H8O4)3(C6H4N3)3]·5.5H2O, has been synthesized under solvothermal conditions and characterized by single-crystal X-ray structure determination, IR spectroscopy, elemental analysis, TGA, and powder X-ray diffraction. Crystal structure analysis shows that the complex is a 3D framework with hexagonal channels accommodating guest water molecules. Furthermore, the photoluminescence properties and nitrogen gas adsorption of this complex were investigated. The complex exhibits strong photoluminescence emission, and its open cavities possess nitrogen adsorptive ability.

Three novel 3D microporous heterometallic coordination polymers, [LnZn(imdc)(ip)(H2O)2]·3H2O [Ln = Nd (1), Eu (2), Gd (3); H3imdc = imidazole-4,5-dicarboxylic acid; ip = isophthalate], have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that compounds 1–3 are isomorphous and crystallize in the monoclinic space group P21/c. The crystal structures constructed from Zn-imdc step-like chains and 2D [LnZn(imdc3−)]n layers and ip ligand, which giving rise to a 3D framework that consists of two types of 1D open channels, with 5.2 × 8.6 Å channels along the a axis and 8.6 × 10.2 Å channels along the b axis. The luminescence properties of complex 1 and 2 have also been investigated.The crystal structures constructed from Zn-imdc step-like chains and 2D [NdZn(imdc3−)]n layers and ip ligand, which giving rise to a 3D framework that consists of two types of 1D open channels, with 5.2 × 8.6 Å channels along the a axis and 8.6 × 10.2 Å channels along the b axis.Research highlights► Three novel 3D microporous heterometallic coordination polymers have been synthesized. ► 3D framework consists of two types of 1D open channels. ► Complexes constructed from H3imdc and Ln–Zn heterometallic system have not been reported.

Four novel organodisulfonate coordination polymers ranging from 0D cluster, 1D chain, 2D layer to 3D framework, {[Eu2(phen)4(nds)2(OH)2(H2O)2]·2H2O}n (1), {[Eu(phen)2(nds)0.5(OH)(H2O)]·0.5nds}n (2), {[Eu2(phen)4(nds)3(H2O)2]·7H2O}n (3), {Eu(phen)(nds)(OH)}n (4) (nds = 2,6-naphthanlenedisulfonate; phen = 1,10-phenanthroline), were synthesized by tuned stoichiometric ratio of the reactants and characterized by single crystal X-ray diffraction, elemental analysis, IR and thermogravimetric analysis. These complexes display a broad and strong ligand-centered luminescent emission band, and all of them have long luminescence lifetimes at millisecond order.Four novel organodisulfonate coordination polymers ranging from 0D cluster, 1D chain, 2D layer to 3D framework were synthesized by tuned stoichiometric ratio of the reactants and characterized by single crystal X-ray diffraction, elemental analysis, IR and thermogravimetric analysis, providing example of structure diversities exhibiting different luminescent properties through the same reactants.Highlights► Four novel organodisulfonate complexes have been synthesized. ► The only difference among four compositions is the stoichiometric ratio of the reactants. ► Structural diversities exhibit different luminescent properties.

A series of lanthanide(III)-Ag(I) 4d−4f heterometallic coordination polymers (HCPs) with pcu topology, {[LnIIIAgI(Hbidc)(bidc)(ox)0.5(H2O)]·H2O}n (Ln = Sm 1, Eu 2, Gd 3, Tb 4, Dy 5, Ho 6, Er 7, H2bidc =1H-benzimidazole-5,6-dicarboxylic acid, ox = oxalate), have been synthesized through self-assembly reactions. All seven complexes are isostructural and have three-dimensional 2-fold interpenetrated structures, with both the organic ligand and oxalate groups acting as bridges. These new complexes crystallize with the same unique six-connected three-nodal net described by (108·12·164·182) (10)6 topology. The ferromagnetic properties of complex 3 were investigated. Moreover, complexes 1, 2, 4, and 5 exhibit very strong photoluminescence properties and with long lifetimes in the solid state at room temperature.

Two new 4f–3d heterometallic coordination polymers [Gd2Co(L1)3(ox)(H2O)4]·2.5H2O (1, L1 = pyridine-2,5-dicarboxylate anion, ox = oxalate dianion) and [GdNi(L2)2(ox)0.5(H2O)3]·3H2O (2, L2 = pyridine-2,3-dicarboxylate anion) were successfully synthesized under hydrothermal conditions. In compound 1, one dimensional heterometallic and lanthanide infinite sheets were constructed with sole L1 spacers and L1–ox mixed bridges, respectively. While similar one dimensional heterometallic infinite sheet and normal lanthanide infinite zigzag chain were formed based on sole L2 and L2–ox mixed bridges, respectively in compound 2. Both of the two compounds exhibited new and interesting three dimensional topologies. In addition, the magnetic properties of the two compounds were analyzed via solid-state dc magnetic susceptibility measurements.Two 4f–3d coordination polymers with intriguing 3D topologies were synthesized under hydrothermal conditions, and there are antiferromagnetic interactions between paramagnetic ions in both of the two compounds.

Three novel lanthanide complexes, namely, [Ce(Himdc)(H2imdc)(H2O)3]·H2O (1), {[Dy(Himdc)(Ox)0.5(H2O)2]·H2O}n (2), and {[Nd(Himdc)(Ox)0.5(H2O)2]·H2O}n (3) (H3imdc = imidazole-4,5-dicarboxylic acid, Ox = oxalate), have been successfully prepared by the assembly of lanthanide ions and H3imdc ligand under different synthetic conditions. All of the complexes have been characterized by means of elemental analysis, IR, TG analysis, luminescence spectroscopy as well as single-crystal X-ray diffraction analysis. The 3D supramolecular structure of 1 is constructed from 1D zig-zag chains through the hydrogen bonding interactions. Complex 2 possesses the chair-shaped secondary building units (SBUs) with Dy6(Himdc)4(Ox)2 and meso-helical chains (P + M), resulting in a novel 2D structure based on the linkages of oxalate ligand. Complex 3 also presents 2D layer structure with uninodal 6-connected net topology, but crystallizes in the different space group and owns higher coordination number of the central metal atom than complex 2. The luminescence property of 2 is investigated in the solid state at room temperature.

One new three-dimensional 3d–4f heterometallic coordination polymer, namely, {[EuZn2(imdc)2(C2O4)0.5(H2O)4]·2H2O}n (1) (H3imdc = imidazole-4,5-dicarboxylic acid), has been successfully synthesized by the hydrothermal reactions of Eu2O3, Zn(NO3)2·6H2O, H3imdc, H2C2O4·2H2O and H2O. Single-crystal X-ray diffraction analysis reveals that complex 1 possesses 3D heterometallic framework containing 2D layer based on L–Zn2–L (L = imdc) helical chains and L–EuZn1–L chains. Complex 1 exhibits unprecedented (3,4)-connected four-nodal topology with Schläfli symbol (6·7·8) (6·7·9) (6·72·82·10) (7·82). Moreover, the photoluminescence property of 1 was investigated in the solid-state at room temperature.A novel 3D 3d–4f heterodimetallic coordination polymer was synthesized, which is formed with right-hand helical structure and unique (3,4)-connected four-nodal topology. The title compound displays relatively strong photoluminescence.

Two 3d-4f heterometallic coordination polymers, [GdIII2CuII(pydc)2(CO3)2(H2O)2]·2H2O (1, pydc = 2,5-pyridinedicarboxylate dianion) and [GdIII4CoIICoIII(μ3-OH)3(μ3-O)(pydc)6(H2O)5]·8H2O (2) have been synthesized under hydrothermal conditions. In compound 1, 2D {[Gd2(CO3)2]2+}n sheets are connected by [Cu(pydc)2]2− bridges, which give rise to the formation of a sandwich-like framework. Compound 2 exhibits a 3D framework constructed by Gd4 clusters, Co2 subunits, and pydc spacers. The solid-state dc magnetic measurements reveal antiferromagnetic behaviors of 1 and 2 in both compounds.

Two new lanthanide coordination polymers H2N(CH3)2·[EuIII2(L1)3(L2)] (1, L1=isophthalic acid dianion, L2=formic acid anion) and [LaIII(2,5-PDC)(L2)](2, 2,5-PDC=2,5-pyridinedicarboxylate dianion) were synthesized under solvothermal conditions. It is of interest that the formic ligand (L2) is not contained in the stating materials, but arises from the water molecule-enhanced CO2 insertion during the solvothermal process. Both of the two compounds exhibit complicated three dimensional sandwich-like frameworks.Two new lanthanide coordination polymers involving water molecule-enhanced CO2 insertion resulting in the formation of formic anion and dimethylammonium cation were synthesized under solvothermal conditions.

Two novel 3-D coordination compounds, Nd2[C6(COO)6](H2O)6 (1) and Ho2[C6(COO)6](H2O)6 (2), were hydrothermally synthesized from mellitic acid and neodymium perchlorate (or holmium perchlorate) in the alkaline aqueous solution and characterized with elemental analysis, TG, IR spectrum, and single crystal X-ray diffraction. The two compounds were isostructural and crystallized in the orthorhombic system, space group Pnnm, with a=1.3531 (4) nm, b=0.6687 (2) nm, c=1.0224(3) nm, V=0.92523(5) nm3, Z=4, D=2.630 g/cm3, F(000)=696.0, Goof=1.052. Final R indices [I >2Σ(I)]: R1=0.0195, wR2=0.0382 for 1; a=1.3411(2) nm, b=0.6586(1) nm, c=1.0116(2) nm, V=0.8935(3) nm3, Z=4, D=2.877 g/cm3, F(000)=724.0, Goof=1.061. Final R indices [I >2Σ(I)]: R1=0.0200, wR2=0.0479 for 2. In the two compounds 1 and 2, the mellitic acid ligand, in which all the carboxylate groups were deprotonated, had only one kind of coordination mode to bridge metal ions to form four-connected three-dimensional diamondiod networks.