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The simple solvothermal self-assemble of CuI, 1,4-bis(2-methyl-1H-imidazol-1-yl)butane (L1) and HI in a C2H5OH solvent at pH = 2 created a new H2(L1)2+-templated 1-D chained iodocuprate(I) [H2(L1)][Cu3I5] 1. The crystal data reveal that the Cu-I chain mode in 1 is rare. Two folded Cu2I2 cores first aggregate into a trinuclear cluster by sharing an edge. Then the extra I− ions doublely bridge these trinuclear clusters into the title 1-D chain of 1. Synchronously, a non-folded Cu2I2 cluster is formed. In 1, all of the Cu···Cu distances are smaller than 2.8 A. The investigation on photoluminescence property indicates that with the decrease of the temperature, the photoluminescence emission for 1 exhibits a minor change from the green-yellow light (298 K) to yellow light (77 K). This means that 1 might possess the fluorescent thermochromic property.

Under the hydrothermal conditions, the simple self-assembly between Cd2+, 2,3,5,6-pyridinetetracarboxylic acid (L1′), and N2H4 created a L12−-based Cd2+ coordination polymer [Cd(L1)(N2H4)] · 2H2O (L12− = 2,3,5,6-pyridinetetracarboxylhydrazidate) 1. H2L1 derived from the in situ acylation of L1′ with N2H4. X-ray single-crystal diffraction analysis reveals that 1 possesses a 1-D chained structure co-bridged by L12− and N2H4, where a castellated CdO single-chain is observed. It is noteworthy that between the L12− molecules, two types of cyclic hydrogen-bonded synthons are found. Via these weak intermolecular interactions, 1 self-assembles into a 3-D porous supramolecular network (window size: 8 × 7 A2). The tetrahenuclear water clusters with a tetrahedral structure are observed in the pores.

At pH 2, the simple room-temperature self-assemblies between Cd2+ salts, SCN− and organic bases created one new thiocyanatocadmate as [H2(L1)][Cd2(SCN)6] (L1 = 1,4-bis(2-methyl-1H-imidazol-1-ylmethyl)benzene) 1, and two new halo-thiocyanatocadmates as [H2(L2)][CdI2(SCN)2]·H2O (L2 = 3,5-bis (4-pyridyl)-1,2,4-triazole) 2, and [CdCl(SCN)(L3)] (L3 = 3-pyrazinyl-1,2,4-triazole) 3. X-ray single-crystal diffraction analysis reveals that (a) in 1, with H2(L1)2+ as the countercation, the SCN− groups tri-bridge the Cd2+ centers into a 1-D chained thiocyanatocadmate; (b) 2 is only a mononuclear iodo-thiocyanatocadmate, and H2(L2)2+ acts as the countercation. But via the π···π and Npyridyl–H···NSCN interactions, H2(L2)2+ and CdI2(SCN) 2 2− aggregate together to form a 1-D supramolecular tube. Amongst the tubes, a chained water cluster with a zig-zag shape is observed; (c) 3 is an organically extended chloro-thiocyanatocadmate. Note that the report on this type of material is rather rare. It possesses a 3-D network structure with a dia topology, in which a castellated CdCl+ single chain is observed. L3 and Cl− act as a mixed bridge, whereas SCN− just serves as a terminal ligand in 3. The photoluminescence analysis indicates that the title compounds 1–3 all emit light (green light for 1, blue light for 2 and 3), which should be attributed to the ligand-centered electronic excitations.

Two supramolecular compounds [Cu(imz)2][Cu(phen)(imz)]2{[Cu(phen)]2[PMo6 VIMo6 VV2 IVO42]}(1) and [Co2(2,2′-bpy)4(C2O4)][Co(2,2′-bpy)3][PMo7 VIMo5 VV2 IVO42](2,2′-bpy)0.5·H2O(2)(phen=1,10′-phenanthroline, imz= imidazole, 2,2′-bpy=2.2′-bipyridine) have been synthesized hydrothermally and characterized by elemental analyses, infrared spectrum, UV-Vis, X-ray photoelectron spectroscopy(XPS), electron spin resonance(ESR) spectra, thermogravimetry analyses and single crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that both the compounds represent the examples of compounds based on the bi-capped Keggin polyoxoanion {PMo12V2O42} and transition metal mixed-organic-ligand coordination complexes. Compound 1 consists of bi-capped Keggin polyoxoanion [PMo12V2O42]5− supported copper coordination groups, which are further inter-connected with two types of copper complex fragments forming a 3D supramolecular framework via π⋯π stacking, C-H⋯O and N-H⋯O hydrothermal bonding interactions. Compound 2 is a new hybrid consisted of polyoxoanion [PMo12V2O42]4−, [Co2(2,2′-bpy)4(C2O4)]2+ and [Co(2,2′-bpy)3]2+. There are no direct interactions in compound 2, but the polyoxoanions together with two different cobalt complex groups construct a 3D supramolecular network through C-H⋯O hydrogen bonding interactions.

Having been designed via bottom-up strategy based on density functional theory(DFT) calculations, a complex of ytterbium(II) with pyridyl amido ligand was successfully synthesized by one-pot reaction in laboratory. DFT calculation shows that pyridyl amido ligands can stabilize the complex via steric and electron effect. This success in integrating computation with synthesis will inspire more explorations in the development of a new complex in lanthanide chemistry.

Two new compounds, [Ni(en)2]{[Ni(en)2]2[MoVI 6MoV 2VIV 8O40(SiO4)]}[(NH2)2(C2H4)2NH]·2H2O(1) and [Ni(en)2]{[Ni(en)2]2[MoVI 5MoV 3VIV 8O40(VO4)]}(en)·H2O(2)(en=ethylenediamine), have been hydrothermally synthesized and characterized by elemental analysis, infrared(IR), X-ray photoelectron spectroscopy(XPS), electron spin-resonance(ESR) and thermogravimetric(TG) analysis and single-crystal X-ray diffraction(XRD) analysis. Both the compounds exhibit a 1D chain composed of bi-supporting tetra-capped Keggin clusters and nickle coordination fragments. The 1D chains are further assembled into a 3D supramolecular network with different packing modes via hydrogen bonds. The magnetic susceptibility of compound 1 demonstrates the presence of antiferromagnetic interactions.

Under the hydro(solvo)thermal conditions, the reactions of metal halides with organic N-heterocyclic molecules produced three new organically modified metal halides [tmbp][Cu2Br4] (tmbp2+ = N,N,N′,N′-tetramethyl-4,4′-bipiperidinium) 1, [H2(dmbpp)][Pb2I6] (dmbpp = dimethyl-1,3-bis(4-piperidyl)propane) 2 and [PbI2(bpp)] 3 (bpp = 1,3-bis(4-pyridyl)propane). It is noteworthy that tmbp2+ in compound 1 originated from the in situ alkylation of bp with CH3OH (bp = 4,4′-bipiperidine). The mechanism study indicates that H+ and Br− play a key role in the alkylation reaction. X-ray single-crystal diffraction analysis revealed that (i) compounds 1 and 2 are the organically templated halometallates. Both possess the 1D chain structures. The 1D chain of compound 1 can be regarded as a linear arrangement of CuBr4 tetrahedra by sharing the edges, whereas that of compound 2 can be considered as an endless extension of PbI6 octahedra by sharing the faces; (ii) compound 3 is the 1:1 adduct of PbI2 and bpp. The PbI2 chain shows a linear shape. Bpp serves as the connector, propagating the PbI2 chains into a 2D layer network of compound 3.

At the ambient condition, the simple self-assembly between ZnI2, KI, and dabco in acidic H2O/C2H5OH solution produced a tetranuclear iodine cluster with diprotonated dabco as the cation [H2dabco](I4) (dabco = 1,4-diazabicyclo[2,2,2]octane) 1. But the same precursors reacted under the solvothermal condition, producing a chained iodine cluster polymer with dedabco2+ as the cation [dedabco](I3)2 (dedabco2+ = N,N′-diethyl-1,4-diazabicyclo[2,2,2]octane) 2. Note that dedabco2+ originated from the solvothermal in situ N-alkylation of dabco with C2H5OH solvent in acidic KI solution.

Based on the hydrothermal in situ acylation reaction of 4,4′-biphthalic acid (bpha) with N2H4·H2O, a new acylhydrazidate-bridged 1-D chained Cd2+ coordination polymer [Cd(BPTH)(phen)]·3.75H2O (BPTH = 4,4′-biphthalhydrazidate, phen = phenanthroline) was synthesized, and characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction (XRD), thermogravimetric analysis and single-crystal XRD. With ancillary phen molecules, the BPTH molecules link the Cd2+ centers into a 1-D staircase chain structure of compound 1 based on the Cd2O2 clusters. Based on the hydrothermal in situ acylation reaction of 4,4′-biphthalic acid (bpha) with N2H4·H2O, a new acylhydrazidate-bridged 1-D chained Cd2+ coordination polymer [Cd(BPTH)(phen)]·3.75H2O (BPTH = 4,4′-biphthalhydrazidate, phen = phenanthroline) was synthesized. With ancillary phen molecules, the BPTH molecules link the Cd2+ centers into a 1-D staircase chain structure of compound 1 based on the Cd2O2 clusters.

Under the hydrothermal conditions, the simple self-assemblies of the Pb2+ salts, NaBr/KI and dabco in acidic aqueous solutions created two protonated dabco-templated chained haloplumbates [H2dabco][Pb2Br6]·H2O 1 and [Hdabco][PbI3]·H2O 2 (dabco = 1,4-diazabicyclo[2,2,2]octane). Compound 1 possesses the 1-D double-chain structure based on the Pb2Br9 subunits, while compound 2 shows the simple 1-D single-chain structure based on the PbI6 octahedra. Ultraviolet–visible spectrum analysis indicates that compound 2 is the potential semiconductor material. [Under the hydrothermal conditions, the simple self-assemblies of the Pb2+ salts, NaBr/KI and dabco in acidic aqueous solutions created two protonated dabco-templated chained haloplumbates [H2dabco][Pb2Br6]·H2O 1 and [Hdabco][PbI3]·H2O 2. Compound 1 possesses the 1-D double-chain structure based on the Pb2Br9 subunits, while compound 2 shows the simple 1-D single-chain structure based on the PbI6 octahedra. UV–vis spectrum analysis indicates that compound 2 is the potential semiconductor material.]

In methanol solutions, two types of organic N-donor ligands bta and dabco (bta = benzotriazole; dabco = 1,4-diazabicyclo[2,2,2]octane) were selected to react with CuI under the solvothermal conditions, creating two new copper(I) iodides as one-dimensional (1D) chained [CuI(bta)] 1 and tetranuclear [(mdabco)2Cu4I6] (mdabco = N-methyl-1,4-diazabicyclo[2,2,2]octane). Note that mdabco derived from the solvothermal in situ alkylation reaction between dabco and methanol solvent. The photoluminescence analysis revealed that compound 2 is a potential fluorescence material with maximum emission at 506 nm. The structural characterization of two new copper(I) iodides as chained [CuI(bta)] 1 and tetranuclear [(mdabco)2Cu4I6] (bta = benzotriazole; mdabco = N-methyl-1,4-diazabicyclo[2,2,2]octane) 2 were reported. Mdabco derived from the solvothermal in situ alkylation reaction between dabco and methanol solvent. .

Two new arsenic–vanadium clusters, [Co(2,2′- bpy)3]2[As8V14O42(H2O)] · 3H2O (1), [2,2′-bpy][Ni(2,2′-bpy)3]2[As8V14O42(H2O)] · 3H2O (2) (2,2′-bpy=2,2′-bipyridine), have been hydrothermally synthesized and characterized by IR, elemental analysis, UV–VIS, EPR, TGA, XPS, and single crystal X-ray diffraction analysis. Crystal data: 1, triclinic, P1, a=14.368(3) A, b=16.753(3) A, c=24.632(5) A, α=94.15(3)°, β=93.16(3)°, γ=113.05(3)°, Z=2; 2, monoclinic, P21/c, a= 30.2150(4) A, b=14.0690(3) A, c=26.0536(3) A, β=106.8960(10)°, Z=4. X-ray crystallographic studies showed that crystals 1 and 2 are both composed of discrete cluster anion [As8V14O42(H2O)]4− and transition metal coordination complexes [M(2,2′-bpy)3]2+ (M=Co or Ni). Interestingly, compound 2 contains another neutral organic space filler of 2,2′-bpy. To the best of our knowledge, compounds 1 and 2 are the first examples of structurally characterized vanadium/2,2′-bpy/arsenate polyoxometallates.

The hydrothermal reactions of CuBr2, CuX (X=Br, I), and phen (phen=1,10-phenanthroline, C12H8N2) have lead to the syntheses of two novel complexes of one-dimensional [Cu4Br2I3(phen)2] n 1 and trinuclear discrete cluster Cu3Br3(phen)2 2. Both compounds were characterized by singe-crystal X-ray diffraction. Crystal data for 1. Monoclinic, space group P2 1/c with a=14.054(3) A, b=13.700(3) A, c=15.920(3) A, β=114.16(3)°, Z=2; 2. Monoclinic, space group C2/c with a=10.040(2) A, b=14.516(3) A, c=16.319(3) A, β=94.29(3)°, Z=6.

Three novel binuclear CoIIcomplexes, [Co2(TAE)-(phen)4](ClO4)2·3H2O(1),[Co2(TAE)(Nphen)4](ClO4)2 ·4H2O(2) and [CO2(TAE)(bipy)4](ClO4)2·H2O(3) (TAE=tetraacetylethene dianion, phen=1,10–phenanthroline, Nphen=5–nitro·1,10–phenanthroline, bipy =2,2′-bipyridy1), have been synthesized and characterized by elemental analysis, i.r., molar conductance and electronic reflection spectra. The complexes are proposed to contain tetraacetylethene dianion bridged structures and two CoII ions. The variable-temperature magnetic susceptibility of complex (1) was measured in the 4–300 K range. The magnetic coupling parameter is consistent with antiferromagnetic exchange between the two CoII centres and the data fit a binuclear magnetic exchange model based on the Hamiltonian operator (Ĥ = −2 JŜ1Ŝ2, S1=S2=3/2), giving the antiferromagnetic coupling parameter of 2J=−1.55cm−1.

The Cr2(Sq)2(OH)2·6H2O complex (Sq=squarate), synthesized by a hydrothermal method, was characterized by elemental analysis, i.r. and electronic reflection spectra. The variable-temperature magnetic susceptibility of the complex was measured over the 77–300K range. The magnetic coupling parameter is consistent with an antiferromagnetic exchange model based on the Hamiltonian operator (H^ = -2JS^1S^2, where S1 = S2 = 3/2), giving the antiferromagnetic coupling parameter of 2J = -11.5 cm−1.