Search

Through employing the hydrothermal in situ acylation of organic acids with N2H4, six L12−-based coordination polymers, [M(L1)(H2O)]·H2O (M2+ = Cd2+1, Zn2+2, Fe2+3, Mg2+4; H2L1 = 6,6′-(perfluoropropane-2,2-diyl)bis(2,3-dihydrophthalazine-1,4-dione)), [Pb(L1)] 5, and [Er2(L1)2(ox)(H2O)2]·5H2O (ox = oxalate) 6, were obtained. X-ray single-crystal diffraction analysis reveals that (i) the L12−-based Cd2+, Zn2+, Fe2+ and Mg2+ coordination polymers are isostructural, and they possess a 2D single-layer network structure with a 44 topology; (ii) 5 possesses a 3D network structure, which is constructed from the dinuclear Pb2O812− clusters by the L12− molecules; (iii) 6 possesses a 2D double-layer network structure. Two 2D single-layer networks (the same as those in 1–4) are supported by ox to form this 2D double-layer network. 1D channels (428.9 A3 for total potential solvent-accessible void volume) are observed in 6. 1, 2, 5 and 6 are found to emit blue light, corresponding to the L12−-centered electronic excitation. Based on the photoluminescence properties, their sensing ability towards the inorganic Cr2O72− anion was investigated. 5 exhibits the better sensing ability towards Cr2O72−. The heavy-atom effect should play a key role.

A series of compounds based on vanadate, [Zn(1,10-phen)3][Zn(dap)2]0.5[Zn(dap)2(H2O)]2[VV6VIV10O38Cl]·2H2O (1), [Ni(im)6]3[VV7VIV8O36Cl]·17H2O (2), [Zn(2,2′-bpy)3]2[H2VV10O28]·6H2O (3), [Fe(Phen)3]3[V16O39Cl]·8.5H2O (4), [Zn(2,2′-bpy)]3[V15O36Cl] (5), [Co(2,2′-bpy)]3[V15O36Cl] (6), [Ni(en)2]3[V18O42Cl]·18H2O (7), [Cd(2,2′-bpy)2]2[V4O12]·0.5H2O (8), [Ni(2,2′-bpy)3]2[V4O12]·11H2O (9), [Zn(2,2′-bpy)3][V4O12]·11H2O (10) and [Ni(phen)3]2[V4O12]·12H2O (11) (1,10-phen = 1,10-phenanthroline, dap = 1,2-propanediamine, 2,2′-bpy = 2,2′-bipyridine, im = imidazole), has been synthesized under hydrothermal conditions and characterized using IR, UV-vis, XRD, ESR, elemental analysis and crystal structure analysis. Out of the eleven compounds, 1–3 and 11 are novel. Compound 1 is based on [V16O38Cl]7− anions and [Zn(dap)2]2+ and [Zn(dap)2(H2O)]2+ cations, forming a novel dimer of cluster supported coordination complexes. Compound 2 has a supramolecular structure based on [V15O36Cl]6− anions (V15) and [Ni(im)6]2+ cations. Compound 3 also has a supramolecular structure, which is constructed from [H2V10O28]4− and [Zn(2,2′-bpy)3]2+ cations. Compound 11 is formed by [V4O12]4− clusters and [Ni(phen)3]2+ cations. Compounds 4–10 are also based on vanadate and are not new compounds. Here, we investigate the catalytic properties of these eleven compounds, and the photocatalytic properties of some of these compounds.

Seven novel compounds based on arsenic–vanadium clusters [Ni(im)(2,2′-bpy)]2[Ni(im)2]2[Ni(2,2′-bpy)][As8V14O42(H2O)] (1), [Ni(2,2′-bpy)3][Ni(im)2]0.5[Ni(2,2′-bpy)(im)][As8V14O42(H2O)] (1a), [Ni(2,2′-bpy)(phen)][Ni(2,2′-bpy)2][As8V14O42(H2O)]·H2O (2) and [Ni(2,2′-biim)(2,2′-bpy)2]2[As8V14O42(H2O)]·6H2O (3), [Cd(2,2′-bpy)(phen)2]2[As8V14O42(H2O)]·4H2O (4), [Cd4(phen)4(ox)(H2O)6][As6V15O42(H2O)]·2H2O (5) and [Co2(phen)4(ox)][H2As8V14O42(H2O)]·(apy)2·2H2O (6) (Him = imidazole, phen = 1,10-phenanthroline, 2,2′-biim = 2,2′-biimidazole, apy = 2-aminopyridine) have been synthesized and characterized by IR, UV-vis, XRD, TG, CD spectrum, elemental analysis and single-crystal X-ray diffraction analysis. Crystal analysis reveals that compound 1 is the first example of a hybrid compound constructed from polyoxometalates and transition metal mixed-organic-ligand complexes of negatively charged nitrogen-containing ligands and neutral nitrogen-containing ligands. Compound 1a is the first example of a POM supported TMC which is formed via arsenic–metal contact. Compound 2 is a chiral compound which exhibits a novel 1-D triple-chain structure constructed from [As8V14O42(H2O)]4− clusters, a type of chiral transition metal mixed-organic-ligand complex and a type of chiral transition metal complex. Compounds 3 and 4 are supramolecular compounds which are formed by [As8V14O42(H2O)]4− clusters and transition metal mixed-organic-ligand complexes, respectively. Compounds 5 and 6 are constructed from arsenic–vanadium clusters and transition metal complexes of nitrogen-containing ligands and oxalic groups. The catalytic properties of compounds 1 and 2–6 have been investigated and we found that the transition metal mixed-organic-ligand complexes have dramatic influences on the catalytic properties of catalysts.

Five new vanadoantimonates [Cd(en)3]3[Sb6V15O42(H2O)]·8H2O (1), [Ni(en)3]2[H2Sb6V15O42(H2O)]·5H2O (2), [Co(en)3]2[H2Sb6V15O42(H2O)]·5H2O (3), [H4Sb8V14O42(H2O)]·5H2O (4) and [Co(enMe)3]2[Sb8V14O42(H2O)]·4H2O (5) (en = ethylenediamine, enMe = 1,2-propanediamine) have been obtained under hydrothermal conditions and characterized by IR, UV-Vis, XRD, ESR and CD spectroscopy. Compound 1 is a chiral compound constructed from [Sb6V15O42(H2O)]6− (Sb6V15) and [Cd(en)3]2+. Compounds 2 and 3 are isostructural and isomorphous. Both compounds are chiral, each of which contains a 2-D inorganic layer formed by [H2Sb6V15O42(H2O)]4−via V–O⋯Sb contacts. Compound 4 contains a 2-D inorganic layer formed by [H4Sb8V14O42(H2O)], of which [H4Sb8V14O42(H2O)] is directed by both V–O⋯Sb and Sb–O⋯Sb interactions. Compound 5 contains a 1-D zigzag chain structure formed by [Sb8V14O42(H2O)]4− (Sb8V14) via Sb–O⋯Sb contacts.

Four new organic–inorganic hybrid compounds, namely, [Cu3(4,4′-bpy)3][HSiW12O40]·(C3H4N2) (1), [Cu3(4,4′-bpy)3][PMo12O40]·(C5H6N2)·0.5H2O (2), [Cu2(4,4′-bpy)2][HPMo12O40]·(C5H6N2) (3) and [Cu(Phen)(4,4′-bpy)(H2O)]2[PW12O40]·(4,4′-bpy) (4) (C3H4N2 = imidazole, C5H6N2 = 2-aminopyridine, bpy = bipyridine, Phen = 1,10-phenanthroline), have been synthesized and characterized by IR, UV-vis, powder XRD, cyclic voltammetry analysis, photoluminescence analysis, elemental analyses and single crystal X-ray diffraction. The four compounds represent new examples of secondary organic moiety templated frameworks constructed from Keggin polyanions, metal ions and organic ligands. Compounds 1 and 2 present 3-D framework structures; compound 3 exhibits a 1-D ladder-like structure and compound 4 shows a 2-D layered framework structure. It is noted that the packing structures of compounds 1 and 2 are almost identical; however, the crystal space groups and cell parameters of the two are thoroughly different. Such a phenomenon has also been observed between compound 3 and a compound recently reported by us. Compound 4 is the first framework structure constructed from polyoxometalates, metal ions and mixed organic ligands. In addition, all the four frameworks are combined with dissociated organic moieties as templates.

Six new hybrid compounds based on polyoxometalates and transition metal complexes, [SiW12O40][Ag4(2,2′-bpy)4(4,4′-bpy)3]·2H2O (1), [SiMo12O40][Cu(2,2′-bpy)(H4,4′-bpy)2(H2O)][H4,4-bpy] (2), [PMo12V2O42][Cd2(Phen)2(4,4′-bpy)2(H2O)2(C2O4)]·2H2O (3), [PMo12V2O42][Cu2(4,4′-bpy)2][Cu2(Phen)(4,4′-bpy)2]·3H2O (4), [SiMo12V2O42][Cu2(Phen)2(4,4′-bpy)]2 (5) and [GeMo12V2O42][Cu2(Phen)2(4,4′-bpy)]2 (6) (bpy = bipyridine, Phen = phenanthroline), have been synthesized and characterized. Compound 1 contains a discrete tetranuclear silver-2,2′-bpy-4,4′-bpy complex; compound 2 is the first example where the polyoxometalate supports a metal–aqua–2,2′-bpy-4,4′-bpy complex; it should be noted that the complex contains a 2,2′-bpy and two 4,4′-bpy ligands; compound 3 is the first hybrid compound based on polyoxometalates and metal–aqua–4,4′-bpy–oxalic–phenanthroline complexes; and compound 4 is a novel hybrid compound based on polyoxometalates, extended metal–4,4′-bpy complexes and extended metal–4,4′-bpy–phenanthroline complexes together. Compounds 5 and 6 are isomorphous and isostructural; both exhibit a supramolecular structure constructed from bicapped Keggin POMs and metal–4,4′-bpy–phenanthroline complexes.

Three new arsenic–vanadium compounds, [As8V14O42(H2O)][Cu(2,2′-bpy)2]4 (1) [As8V14O42(H2O)][Cu(1,10-Phen)2]4 (2) and [As8V14O42(H2O)][Ni(Biim)3]2·6H2O (3) (2,2′-bpy = 2,2′-bipyridine, 1,10-Phen = 1,10-phenanthroline and Biim = 2,2′-biimidazole), have been prepared hydrothermally and characterized by IR, UV-Vis, XRD, XPS, and single-crystal X-ray diffraction analyses. X-ray crystallographic studies showed that compounds 1–3 are all based on the cluster anion [As8V14O42(H2O)]4−. However, the crystal structures of the three are thoroughly different. It is obvious that the transition metal complex building blocks are the vital factor for the packing structures of the three. We carefully discussed the influence of transition metal complex building blocks on the crystal structures. Also we analyzed the catalytic properties of the compounds and discussed the influence of the crystal structures of transition metal complexes on the catalytic properties.

Five hybrid compounds constructed from polyoxometalates, transition metals and organic ligands [Ni2(4,4′-bpy)5(H2O)2][HBW12O40]·5H2O (1), [Ni2(4,4′-bpy)5(Cl)2][H2SiW12O40]·3H2O (2), [Ni2(4,4′-bpy)5(Br)2][H2SiW12O40]·3H2O (3), [SiW12O40]3[Cu2(4,4′-bpy)7]·(H24,4′-bpy)2·4H3O·2H2O (4) and [SiW12O40]3[Cd2(4,4′-bpy)7]·(H24,4′-bpy)2·4H3O·2H2O (5) have been prepared and characterized by IR, UV-vis, XPS, XRD, TG, circular dichroism, second order nonlinear optical (NLO) measurements, photoluminescent measurements and single crystal X-ray diffraction analyses. The X-ray diffraction analyses reveal that the five compounds all exhibit novel framework structures constructed from polyoxometalates, transition metals and organic ligands. The compounds 1, 2, and 3 are isomorphous and compounds 4 and 5 are isomorphous, too. There are two main differences among the first three compounds. The first difference of the three is the central atom of the Keggin ions: it is B atom for compound 1, and Si atom for compounds 2 and 3. The second difference of the three is the monodentate ligand coordinating to the Ni ions: it is water molecule for compound 1, chloride ion for compound 2 and bromide ion for compound 3. The difference between compounds 4 and 5 is the transition metal centre of the frameworks. In addition, compounds 4 and 5 are the first examples of compounds containing both Keggin ion and pseudo-Keggin ion.

Five new hybrid compounds constructed from polyoxometalates and transition metal coordination complexes with lower positive charge: [PW11CuO39][Cu(bpy)2]5 (1), [BW12O40][Cu(bpy)2]5 (2) [BW12O40][Cu(Phen)2]3[Cu(Phen)(H2O)]2·2H2O (3), [SiW12O40][Cu(bpy)2]4 (4) and [PW12O40][Cu(bpy)2]4 (5) have been prepared and characterized by IR, UV-Vis, XPS, XRD and single crystal X-ray diffraction analyses. The packing motif of the [Cu(bpy)2]+ copper coordination complexes in compound 1 exhibits square supramolecular channels running along the a axis, which are then filled by the [PW11CuO39]5− ions. Compound 2 is isomorphours with compound 1. Compound 3 contains a novel 2-D supramolecular layer structure constructed from [Cu(Phen)2]+ copper coordination complexes through π⋯π interactions. The packing motif of the [Cu(bpy)2]+ copper coordination complexes in compound 4 exhibits a supramolecular channel which is different from compound 1. Compound 5 is isomorphours with compound 4.

Four inorganic–organic hybrid materials based on poly(oxomolybdophosphate) cluster building blocks have been obtained by hydrothermal methods. 1 shows a 2-D sheet structure, 2 and 3 possess 1-D chain structures and 4 is the discrete cluster. Crystal structural analysis reveals that the dimensionality and organization of those compounds can be tuned by the pH value of the reaction system. In addition, the fluorescence emissions are analysed of compounds 1, 2 and 4 containing Cd atoms with d10 electronic configuration red-shift along with the increase in the dimensions of those compounds.

Under hydrothermal conditions, at different pH levels adjusted by H2ox (ox = oxalate, C2O42−) or N2H4, the reactions of Zn(CH3COO)2·2H2O, phthalic/3-nitrophthalic acid, N2H4·H2O and triazole/tetrazole afforded four new Zn2+ coordination polymers as [Zn5(OH)2(Hpth)2(pth)2(trz)2] (pth = phthalhydrazidate, trz = 1,2,4-triazolate) 1, [Zn3(OH)2(Hpth)2(datrz)2] (datrz = 3,5-diamino-1,2,4-triazolate) 2, [Zn2(pth)(atez)2] (atez = 5-aminotetrazolate) 3 and [Zn5(OH)2(ox)(apth)2(datrz)2] (apth = 3-aminophthalhydrazidate) 4. The acylhydrazide molecules H2pth and H2apth in compounds 1–4 originated from the hydrothermal in situ acylation of N2H4 with phthalic/3-nitrophthalic acid. When preparing compound 4, the reduction of –NO2 into –NH2 also occurred besides the acylation, creating finally a new acylhydrazide molecule H2apth. The X-ray single-crystal diffraction analysis revealed that (i) in compounds 1, 3 and 4, Zn2+ and pth/apth aggregate into the 1D endless chains. The triazolate/tetrazolate molecules extend the Zn2+-pth/apth chains into the different layer networks of compounds 1 and 4, and a 3D network of compound 3; (ii) in compound 2, the datrz molecules link the Zn2+ ions into a 2D layer network. Pth acts as the ancillary ligand; (iii) ox from H2ox was introduced into the final framework of compound 4; (iv) the acylhydrazide molecules exhibit three types of existing forms in compounds 1–4: the diketo form, the keto-hydroxyl form, and the dihydroxyl form. Of those, the dihydroxyl form was observed for the first time. The solid-state photoluminescence analysis indicated that only compound 4 emits green light, and the others do not emit light.

Two new oxalate-propagated Cd2+–acylhydrazidate coordination polymers [Cd2(ox)0.5(Hpth)(pth)(bpy)2] (ox = oxalate, pth = phthalhydrazidate, bpy = 2,2′-bypyridine) 1 and [Cd2(ox)(pdh)2]·H2O (pdh = pyridine-2,3-dicarboxylhydrazidate) 2 were obtained by simple hydrothermal self-assemblies of Cd(CH3COO)2, aromatic dicarboxylic acids, N2H4, and oxalic acid with or without bpy. The acylhydrazidate molecules (pth, pdh) originated from the acylation of N2H4 with aromatic dicarboxylic acids. X-ray analysis revealed that in both compounds, ox acts as the second linker, extending the metal–acylhydrazidate oligomers (tetranuclear for 1; dinuclear for 2) into the high-dimensional coordination polymers. In compound 1, the monoacylhydrazidate molecule with a −2 oxidation state was observed for the first time. In the solid state, only compound 2 emits light, while in an aqueous solution, both compounds emit light. The density functional theory (DFT) calculations indicate that whether in the solid state or in an aqueous solution, the emissions for compound 2 are both assigned to the charge transfer within the pdh molecule, corresponding to the charge transfer from the π* orbitals of the pyridine ring moiety to the π orbitals of the acylhydrazidate ring moiety. The solvent effect of water causes the blue shift from 525 nm to 405 nm. The blue-light emission (465 nm) for compound 1 in an aqueous solution is assigned to the charge transfer between the pth molecules, corresponding to the charge transfer from the π* orbitals of the benzene ring moiety of one pth molecule to the π orbitals of the acylhydrazidate ring moiety of another pth molecule. The Cd2+ center provides the path for charge transfer.

In acidic alcohol/aqueous solution, simple solvo(hydro)thermal self-assembly between Pb(II) salts, KI and pip/dabco (pip = piperazine; dabco = 1,4-diazabicyclo[2,2,2]octane) created three new organically templated iodoplumbates as the chained [H2dppip][Pb2I6]·H2O 1 and [H2depip][Pb2I6]·H2O 2 and the layered [H2dabco][Pb3I8] 3 (dppip = N,N′-dipropylpiperazine; depip = N,N′-diethylpiperazine). Note that dppip/depip were derived respectively from the solvothermal in situ N-alkylation reactions of pip with ethanol/propanol in acidic KI solution. Ultraviolet-visible (UV-vis) spectrum analysis indicates that the three compounds are all potential semiconductor materials with energy gaps of 3.46 eV for 1, 3.02 eV for 2 and 3.31 eV for 3.

Seven new compounds based on polyoxometalates and metal halide clusters have been synthesized and characterized by IR, XPS, UV-vis, XRD, elemental analyses and single crystal X-ray diffraction analyses. Compounds 1, 2, 3 and 4 are hybrids based on polyoxometalates and ennea-nuclear metal halide clusters, which are isomorphous to the compounds we reported recently. Compounds 5–7 are new examples of hybrids based on polyoxometalates and metal halide clusters, of which compounds 5 and 6 are the first examples of hybrids based on polyoxometalates and a new kind of hepta-nuclear metal halide cluster and compound 7 is the first example of hybrid based on polyoxometalates and octakaideca-nuclear metal halide clusters. In addition, compounds 2, 3 and 4 are the first examples of hybrids based on polyoxometalates and metal bromide clusters, and compounds 5 and 6 are the second examples of hybrids based on polyoxometalates and metal iodine clusters. Furthermore, compound 7 is the first example of compounds based on POMs and metal halide extended structures.

Under hydrothermal conditions, the simple reactions between metal salts, aromatic polycarboxylic acids (4,4′-diphthalic anhydride ketone, dphahk; 4,4′-sulfoyldiphthalic anhydride, sdpha; pyridine-2,3-dicarboxylic acid, pdca) and N2H4·H2O with or without the presence of phenanthroline·H2O (phen) yielded four di(mono)acylhydrazidate-coordinated Cd2+/Zn2+ compounds as [Cd(DPHKH)(phen)]·1.75H2O 1, [Zn3(DPHKH)2(HDPHKH)2(phen)2]·8H2O 2, [Cd(SDPTH)(phen)(H2O)]·H2O 3 and [Zn(PDH)2(H2O)2] 4 (DPHKH = 4,4′-diphthalhydrazidatoketone hydrazone; SDPTH = 4,4′-sulfoyldiphthalhydrazidate; PDH = pyridine-2,3-dicarboxylhydrazidate). The di(mono)acylhydrazide molecules in the title compounds originated from the hydrothermal in situ acylation reactions of aromatic polycarboxylic acids with N2H4·H2O. It is noteworthy that another kind of hydrothermal in situ reaction was also observed when preparing compounds 1 and 2, namely the nucleophilic addition reaction between the keto group (of dphahk) and N2H4. The photoluminescence analysis indicates that the compounds in the different states (in the solid state or in aqueous solution) may exhibit different emission behaviors.

The room-temperature self-assemblies between CdX2, NH4SCN and organic N-heterocyclic/diamine molecules in acidic C2H5OH/H2O solutions produced six organically templated chained thiocyanato(halo)cadmates [H2bp][CdCl2(SCN)2] 1, [H2bp][Cd(SCN)4] 2, [H2bpp][Cd3Br(SCN)7] 3, [H2bpy][CdBr2(SCN)2] 4, [H2bpe][Cd(SCN)4] 5 and [H2dach][CdCl4] 6 (bp = 4,4′-bipiperidine; bpp = 1,3-bis(4-piperidyl)propane; bpy = 4,4′-bipyridine; bpe = 1,2-bis(4-pyridyl)ethane; dach = 1,4-diaminocyclohexane). Although the organic N-heterocyclic/diamine molecules are diprotonated, they still act as the bridges to extend the inorganic anionic chains into 2-D or 3-D supramolecular networks via the weak hydrogen-bonded interactions with N atoms as the donors/acceptors.

The room-temperature incorporation of the additional inorganic anionic groups SCN− and SO42− into the CdX2-piperazine (pip) system in acidic H2O/C2H5OH solutions generated the first example of a piperazinium-templated 1-D tube-like cadmium–bromothiocyanato sulfate [H2pip]4[Cd3Br8(SCN)2(SO4)2(H2O)]·4H2O 1 and the isostructural 1-D ribboned cadmium–halothiocyanato coordination polymers [CdX(SCN)L] [X− = Br−2, I−3; L = SC(OC2H5)NH2] with the ancillary organic S-donor ligand L. L was derived from the in situ nucleophilic addition reaction between the SCN−group and the C2H5OH solvent.

Three novel supramolecular compounds [PWVI10.5WV1.5O40][Cu(2, 2′-bpy)2]4.5 (1), [CuI(Phen)2]4[CuI5Cl4(Phen)4][PWVI10WV2O40]2·4H2O(2) and [CuI(Phen)2]4[CuI5Cl4(Phen)4][BWVI12O40]2·2H2O(3) (bpy = bipyridine, Phen = 1,10-Phenanthroline) have been synthesized and characterized by IR, UV-Vis, TG, XRD, elemental analyses and single crystal X-ray diffraction analyses. Compound 1 is the first example of a hybrid compound which is constructed from polyoxometalates and supramolecular noncovalent coordination cages. Both compounds 2 and 3 are constructed from two different types of building blocks: polyoxometalates and metal halide fragments.

Two new compounds based on AsIII–VIV polyoxometalates, [HAs6V15O42(H2O)][Cu(enMe)2]2.5·2H2O (1), [H2enMe]2[As8V14O42(H2O)]·3H2O (2), have been hydrothermally synthesized and characterized by IR, UV-vis, ESR, XPS spectra, elemental analyses, magnetic susceptibility studies and single-crystal X-ray diffraction analyses, respectively. X-Ray crystallographic studies reveal that 1 represents the first example of 2D structure constructed from [HAs6V15O42(H2O)]5− anions and transition metal coordination complexes, in addition, it exhibits the first brick-wall-like 2D layer structure constructed from polyoxometalates and transition metal coordination complexes. 2 exhibits a very interesting stacking mode. The study of magnetic susceptibilities demonstrates the presence of antiferromagnetic interactions in both 1 and 2.

Five novel heteropolyanions have been synthesized and characterized by IR, UV-vis, XPS spectroscopy, XRD, and elemental analyses. Single-crystal X-ray diffraction analyses reveal that these five compounds represent novel examples of compounds based on the combination of polyoxometalates, transition metal coordination complexes and organic amines. Of which 1, 2 and 3 exhibit 0D structures of polyoxometalate supported transition metal coordination complexes, while 4 and 5 exhibit novel 1D structures constructed from polyoxometalates and transition metal coordination complexes.

The hydrothermal in situ self-assembly of Pb2+, benzene-1,2,4-tricarboxylic acid (BTCA) and N2H4·H2O created two Pb(II) coordination polymers containing 4-carboxylphthalhydrazidate (CPTH), [Pb(CPTH)(phen)] (phen = 1,10-phenanthroline) 1 and [Pb4(OH)2(H2O)3(CPTH)3]·2H2O 2. CPTH is derived from the in situ acylation reaction of BTCA with N2H4·H2O.

With the protonated piperazine (pip) and triethylenediamine (1,4-diazabicyclo[2,2,2]octane, dabco) as the templates, two chained chlorocadmates [H2pip][Cd2Cl6(H2O)2] 1, [H2dabco][Cd2Cl6]·H2O 2 and two chained cadmium-chloro thiocyanates [H2pip][CdCl3(SCN)]·2H2O 3, [H2dabco]2[Cd3Cl8(SCN)2]·H2O 4 were obtained, and characterized by IR analysis, CHN analysis, TG analysis and X-ray single-crystal diffraction. The 1-D chain structure of compound 1 is the simplest, and can be described as a zigzag infinite extension of Cd octahedra via sharing the edges. Compound 2 shows a double-chain structure, comprising the dinuclear Cd2Cl9 subunits linked together via sharing the corners and the edges. Compounds 3 and 4 are the first examples of a family of organically templated chained cadmium-chloro thiocyanates. Compound 3 shows a linear-chain structure, comprising the Cd2Cl6 dimers by the SCN−groups, whereas compound 4 shows a stepped-chain structure, comprising the hexanuclear Cd6Cl16 subunits by the SCN−groups. Through intramolecular and intermolecular hydrogen-bonded interactions, all the title compounds are self-assembled into the 2-D or 3-D supramolecular networks. The fluorescence spectra show that compounds 1–3 possess fluorescence properties with emission peaks around 370 nm.

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

With Cu6I6 and Cu8I8clusters as 5-connected nodes, a new 3-D network [Cu14I14(dabco)5(py)] (1) (dabco = 1,4-diazabicyclo[2.2.2]octane, py = pyridine) with a two-fold interpenetrated sqp-(44.66) topology has been hydrothermally synthesized. The solid-state luminescence spectrum displays a strong yellow-light emission with λmax = 591 nm at room temperature.

A series of hydrothermal reactions of metallic salts (CoCl2, CdSO4 and ZnCl2), carboxylates (oxalic acid and 1,4-H2BDC) and organic amines (o-PD, Him) have been investigated. Five coordination complexes, [Zn2(bim)4]n (1), Cd(H2bbim)2SO4·1/3(H2O) (2), [Co2(H2bbim)4(bbim)]Cl2 (3), [Co(Hbim)(Him)(C2O4)]n (4) and [Zn(H2bbim)(1,4-BDC)]n (5) (o-PD = o-phenylenediamine, Hbim = benzimidazole, H2bbim = 2,2′-bisbenzimidazole, Him = imidazole, 1,4-H2BDC = 1,4-benzenedicarboxylic acid), were prepared and characterized by elemental analyses, IR, single-crystal X-ray diffraction, fluorescence and magnetic analyses. Interestingly, two different ligands Hbim and H2bbim were generated via hydrothermal in situ reactions of o-PD and oxalic acid during the formation processes of these compounds. In 1, bim ligands bridge each pair of Zn atoms into a single-stranded helical chain through metal–ligand interactions to generate a 2-D grid-like structure. Complex 2 features a mononuclear structure due to the large steric hinderance of H2bbim ligand. Through N–H⋯Cl hydrogen bonds, the dinuclear units of 3 are alternately arranged to afford a unique 1-D helical chain. Complex 4 exhibits a 1-D zig-zag chain which consists of [Co(Hbim)(Him)]2+ units bridged by oxalate ligands, and 5 displays a 1-D chain structure consisting of Zn(H2bbim)2+ units linked by 1,4-BDC ligands.