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Both ferroelectric and switchable dielectric behaviors are of great academic value and practical significance, but they usually exist alone. If combine the two properties into one compound, it will be more valuable in practical application. In this paper, quasi-spherical (2-bromoethyl) trimethylammonium cation was used to match with [CdBr4 ]2- anion, and a new organic-inorganic hybrid compound ([BrCH2 CH2 N(CH3 )3 ]+2 [CdBr4 ]2- , BETABCdBr) was obtained and carefully characterized. The results indicate that this compound undergoes two continuous reversible phase transition around 342 K and 390 K. It could respectively exhibit ferroelectric and switchable dielectric properties over different temperature range. This work may provide a new clue to explore new types of bifunctional phase transition smart materials to meet various application requirements.

Organic–inorganic hybrid metal halides with temperature-triggered responsive switchable dielectric properties have evoked great attention for their potential application in the field of optoelectronic information. Here, we present a new organic–inorganic hybrid metal halide switchable dielectric material, [(C3H5)2N(CH3)2]2SnCl6 (1), which is obtained by the reaction of diallyldimethylaminium chloride and tin(IV) chloride pentahydrate. Compound 1 exhibits excellent high-temperature switchable dielectric performance and antifatigue. Notably, 1 also exhibits multifunctionality with semiconducting and photoluminescence property. Such a Sn(IV)-based organic–inorganic hybrid with outstanding switchable dielectric, semiconducting, and photoluminescence characteristics will pave a new approach in the development of Sn(IV)-based metal halides with practical applications.

According to “quasi-spherical theory”, structural modifications of spherical organic components have been found to be useful in obtaining ferroelectric or switchable dielectric organic–inorganic hybrid compounds, but how to tailor the spherical organic components is still unclear. In the current work, a prototype spherical tetramethylammonium cation was modified by replacing one of its H atoms with a CH2Br group, rather than with the widely studied Br atom, to obtain a new organic–inorganic hybrid compound, namely [BrCH2CH2N(CH3)3]2+[CuBr4]2− (BETABCuBr). The structure, phase transition, and dielectric and optical properties of BETABCuBr were carefully characterized. Based on these results, BETABCuBr was indicated to undergo a reversible phase transition at about 356 K, mainly due to a piston-like displacive movement of its Cu atom. The extension of the carbon chain was concluded to lead to a change of the phase transition mechanism from the typical order–disorder movement to an unusual displacive movement. We expect the results of this work to contribute to the exploration of new types of phase transition materials.

A new mercury coordination polymer was successfully prepared from HgCl2 and 5-methyltetrazole (Hmtz) and characterized by elemental analysis, thermal analysis, luminescence, theoretical calculation, powder X-ray diffraction and single-crystal X-ray diffraction. Complex 1 is a three-dimensional (3D) hybrid framework constructed from 1D double mercury halide chains and mtz−, and it has an unprecedented ‘AFUQOH’ topological network. Time-dependent density functional theory (TDDFT) calculations reveal that the mechanisms of the fluorescence emission of 1 are dominantly resulted from the metal-to-ligand charge transfer (MLCT) and ligand-to-metal charge transfer (MLCT). Impressively, acentric complex 1 displays not only second harmonic generation (SHG) response but also ferroelectric behaviors.

A series of novel 4f-3d crystalline porphyrinic compounds, {[Co(TPPS)]2[Ln(Histidine)(H2O)][Ln(H3O)3]}n·nH2O (Ln = Sm (1), Eu (2), Dy (3); TPPS = 5,10,15,20-tetra(4-sulfonatophenyl)porphyrinato) with TPPS and histidine as mixed ligands, have been prepared and characterized by single-crystal X-ray diffraction technique. Complexes 1–3 are isomorphous and characteristic of a three-dimensional (3D) framework with the lanthanide ions in two kinds of coordination geometries, i.e., eightfold square antiprism and ninefold monocapped square antiprism. The porphyrin macrocycles adopt a saddle-distorted nonplanar conformation with an embedded cobalt ion binding to four pyrrole nitrogen atoms. As revealed by the photoluminescence measurement, they exhibit blue emission. Variable-temperature magnetic susceptibility reveals that complexes 1–3 are antiferromagnetic. Their FTIR, CV, DPV, and UV/vis results are also studied in detail.

Three new mercury coordination polymers, [HgCl2(Hmtz)]n (1), (2) and [Hg2(mtz)4]n (3), were successfully prepared from HgCl2 and 5-methyltetrazole (Hmtz) and characterized by elemental analysis, thermal analysis, luminescence, theoretical calculation, powder X-ray diffraction and single-crystal X-ray diffraction. The results reveal that 1 and 2 are isomers resulted from different one dimensional (1D) mercury halides chains, and they are all 3D supramolecular structures. Complex 3 possesses a 2-fold interpenetrated diamondoid network with intersecting channels. Time-dependent density functional theory (TDDFT) calculations reveal that the mechanisms of the fluorescence emission are dominantly resulted from the ligand-to-metal charge transfer (LLCT) and partial ligand-to-ligand charge transfer (LLCT) for 1 and 2, but ligand-to-metal charge transfer (LMCT) for 3, which is in good agreement with their different fluorescence spectra and crystal structures. Optical absorption spectra indicate that complexes 1–3 have wide optical band-gaps and can be probably used as wide optical band-gap semiconductor materials.

A new inorganic-organic hybrid complex based on well-defined Keggin-type polyoxometalates and copper-lutidine assemblies, namely, [Cu3(3,5-Lutidine)6(PW12O40)]n (1), has been obtained under hydrothermal conditions and characterized by elemental analysis and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that compound 1 is three-dimensional (3D) supramolecular structure with ‘sql’ topological 2D layer. The photocatalytic experiments indicate that 1 exhibit good catalytic activity for photodegradation of Rhodamine B (RhB) with UV irradiation. The thermal stabilities and fluorescent properties of this complex have also been studied.

A new multifunctional mixed-valence copper(I/II) coordination polymer, {[CuCN][Cu(isonic)2]}n (1) (Hisonic = isonicotinic acid), was synthesized by treating isonicotinic acid and 5-amino-tetrazolate (Hatz = 5-amino-tetrazolate) with copper(II) salts under hydrothermal conditions, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound exhibit noncentrosymmetric polar packing arrangement. It is three-dimensional (3D) framework with (3,5)-connected ‘seh-3’ topological network constructed from metal organic framework {[Cu(isonic)2]}n and the inorganic linear chain{Cu(CN)}n subunits. A remarkable feature of 1 is the rhombic open channels that are occupied by a linear chain of {Cu(CN)}n. Impressively compound 1 displays not only a second harmonic generation (SHG) response, but also a ferroelectric behavior and magnetic properties.

Two new Pb(II) coordination polymers, namely, [Pb(Hpydc)2]n (1), [Pb(Hpydc)2(H2O)]n·2n(H2O) (2) (H2pydc ​= ​2,5-pyridinedicarboxylic acid) have been prepared by the reaction of PbCl2 with pyridinedicarboxylic acid and fully characterized. Compound 1 contains ‘sql’ topological layers built from one-dimensional (1D) Pb-carboxylate infinite chains, and the layers are further packed into a 3D architecture by strong hydrogen bonds interactions. Compound 2 consists of 1D infinite chains containing Pb-dimers. The 3D supramolecular Pb(II) coordination complex of 2 is created by π – π interactions between the pyridine rings of the Hpydc ligands. In addition, solid-state properties of thermal stability and fluorescence for these crystalline materials are also presented. Time-dependent density functional theory (TDDFT) calculations reveal that the mechanism of the fluorescence emissions are dominantly resulted from the ligand-to-metal charge transfer (LMCT) and partial the intraligand π→π∗ and/or n→π∗ transitions for 1 and 2, which are in good agreement with their fluorescence spectra and crystal structure.

We report a new flexible switchable dielectric composite film toward practical application in devices based on β-phase-dominated PVDF modified with single-protonated 1,4-diazabicyclo[2.2.2]octane fluoborate (DabcoHBF4). Our study suggested that incorporating polar molecular filler (DabcoHBF4) into β-phase-dominated PVDF is an effective method to fabricate switchable dielectric thin film, which could avoid sophisticated operation in cultivating bulk crystals of molecular materials. The composite film with 40% of DabcoHBF4 (0.40BF) could exhibit large dielectric change between high and low dielectric states comparable to that of pure DabcoHBF4 at phase-transition temperature. We postulated that the excellent switchable dielectric property of 0.40BF was attributed to the induced orientation alignment of β-phase-dominated PVDF and dielectric confinement effect.

The objective of this study was to investigate five nutrient factors of the forest topsoil (0–20 cm), including pH, soil organic matter (SOM), total nitrogen (STN), available phosphorus (AP), and available potassium (AK). This study adopted the revised Nemerow index method to conduct a comprehensive quantitative evaluation on the soil nutrition contents, and using geostatistical method to address the spatial variability of soil properties in hilly and mountainous regions, southern China. Data were analyzed both statistically and geostatistically on the basis of semivariogram. Our results indicate that the soil is generally acidic, containing rich SOM and STN, but lacks AP and AK. Most of the sub-indexes of fertility were at grade III, showing a middle level. According to the coefficient of variations (CV), the five soil nutrient factors can be ranked in decreasing order as follows: AP > SOM > AK > STN > pH. There were differences between the sub-indexes of fertility, which could be ranked as follows: PSOM > PAK > PSTN > PpH > PAP. The semi-variation functions for the five soil nutrient factors studied here show some spatial structure features, over a range of 23–274 km. All nutrient factors had different nugget-to-sill ratios in each region, which varied from 10 to 50%, suggesting a strong or medium correlation. Thus, it can be concluded that the nutrient spatial distribution of the study area was the result of the combined action of structural factors and random factors, and the factors affecting the soil nutrients of the research area are highly complex. We will develop more targeted research plans about soil nutrients of study area in the next time.

Four new mercury coordination polymers were successfully synthesized under solvothermal conditions and characterized by elemental analysis, IR spectroscopy, thermal analysis, powder X-ray diffraction and single-crystal X-ray diffraction. In these complexes, the chemical valence of mercury is +2, except for complex 1 which is +1. 1 contains [Hg2]2+ metal–metal bonded cores which are bounded by atz− (Hatz = 5-amino-tetrazolate) ligands and features a two-dimensional (2D) uninodal 3-connected ‘hcb’ network. 2 exhibits a trinodal 3D (3,6)-connected ‘apo/alpha-PbO2’ topological net in which 2D [HgCl]nn+ inorganic cation layers are pillared by atz− ligands. In 3, the 2D [HgCl]nn+ cation layers are interconnected by atz− ligands, affording a trinodal 3D (3,6)-connected ‘flu/fluorite’ topological net. 4 is a 3D pillared-layer metal–organic framework based on mixed atz− and isonicotinic ligands, showing a binodal (4,6)-connected ‘fsc’ coordination network. In this work, 1 and 4 were synthesized from an in situ generated tetrazolate ligand, while 2 and 3 were prepared from a commercially available tetrazolate ligand. These results indicate that the final structures of the target complexes will highly depend on the synthetic conditions as well as the preparation methods. Moreover, the photoluminescence properties of these complexes were investigated. Impressively, the non-centrosymmetric complex 3 displays not only a second harmonic generation (SHG) response but also a ferroelectric behavior.

A ferroelectric compound diisopropylammonium bromide (DIPAB) was dispersed into poly(vinylidene fluoride) (PVDF) matrix to form DIPAB/PVDF composite films. The composite film with different content of DIPAB was characterized by IR, XRD, DSC and SEM. The results indicated that soluble DIPAB could be homogeneously dispersed within PVDF matrix to form almost pure β-phase PVDF composite films without obvious agglomeration, and the crystallinity of PVDF polymer increased with increasing content of DIPAB inclusion. DIPAB/PVDF composite films exhibit very high dielectric constants and relatively low dielectric loss. Both dielectric constants and dielectric loss are frequency dependent and increased with increasing DIPAB content. DIPAB/PVDF composite films also exhibit enhanced ferroelectric properties. Incorporating DIPAB into PVDF is a useful way to improve the dielectric and ferroelectric property of PVDF composite films.

Three novel Ln–Hg complexes [Ln(H2O)2(μ-IA)3Hg3Br6]n (Ln = Pr (1), Nd (2), and Er (3); HIA is isonicotinic acid) are synthesized and characterized. They feature three-dimensional (3-D) motifs. Solid-state UV/vis diffuse reflectance spectroscopy found that their band gaps are 4.91, 4.59, and 2.68 eV. It is found that lanthanide ions could adjust the band structures of semiconductors. Their photoluminescence comes from their characteristic emissions of 1D2 → 3H4 of Pr3+, 7F7/2 → 4S3/2 and 4F3/2 → 4I9/2 of Nd3+, and 4I15/2 → 4F7/2 and 4I15/2 → 4S3/2 of Er3+. The CIE chromaticity coordinate is (x = 0.5726, y = 0.4206), (x = 0.7268, y = 0.2732), and (x = 0.2923, y = 0.4317). Their magnetization susceptibility totally obeys the Curie–Weiss equation with antiferromagnetic performances.

The organically-templated uranyl selenite, (H2en)[(UO2)(SeO3)(HSeO3)](NO3)·0.5H2O (1) (en = 1,2-ethylenediamine) was synthesized and characterized by elemental analyses, IR spectroscopy, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 13.170(3) A, b = 11.055(2) A, c = 18.009(4) A, V = 2621.8(9) A3, M = 1316.19, Z = 4, Dcal = 3.334 g·cm–3, μ(Mo-Kα) = 17.998 mm–1, GOF = 1.059, R1 = 0.0263, wR2 = 0.0532 [I>2σ(I)]. The X-ray diffraction analysis reveals that compound 1 has a three-dimensional (3D) supramolecular structure. It contains negatively charged [UO2(HSeO3)(SeO3)]– inorganic anion layers and is balanced by [H2en]2+ cations and NO3– anions located in the interlayers. Furthermore, the photoluminescence properties of 1 were investigated.

Two new zinc compounds, [Zn2(mtz)(nic)2(OH)]n·0.5nH2O (1) and [Zn(phtz)(nic)]2n (2) (Hmtz = 5-methyltetrazole, Hphtz = 5-phenyltetrazole, Hnic = nicotinic acid), have been synthesized by a dual-ligand approach under solvothermal conditions. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, and infrared spectroscopy, respectively. The X-ray diffraction analysis reveals that both compounds exhibit a noncentrosymmetric polar packing arrangement. Compound 1 is a 3D framework constructed from the zigzag chain subunits of [Zn(nic)]+ with a 4-connected “irl” topology. Compound 2 possesses a 2D 4-connected ‘“sql” topology constructed from the linear chain subunit of [Zn(nic)]+, which are linked together with phtz– ligands. Impressively, both of the two compounds display second-harmonic generation response and ferroelectric behaviors. Furthermore, the photoluminescence of the compounds was also investigated.

A dysprosium-zinc porphyrin, [DyZn(TPPS)H3O]n (1) (TPPS = tetra(4-sulfonatophenyl)porphyrin), was prepared through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction analyses. Complex 1 features a three-dimensional (3-D) porous open framework that is thermally stable up to 400 °C. Complex 1 displays a void space of 215 A3, occupying 9.2% of the unit cell volume. The fluorescence spectra reveal that it shows an emission band in the red region. The fluorescence lifetime is 39 µsec and the quantum yield is 1.7%. The cyclic voltammetry (CV) measurement revealed one quasi-reversible wave with E1/2 = 0.30 V. Copyright © 2015 John Wiley & Sons, Ltd.

A new type of ionic ferroelectric based on a chiral salen-type Schiff base erbium(III) complex (ErL) was synthesized by the reaction of erbium nitrate with the ligand N,N′-bis(3,5-dichlorosalicylidene)-(1S,2S)-1,2-cyclohexylenediamine (L). The structures of the ligand L and the complex ErL were determined by single-crystal X-ray diffraction. The results indicated that ErIII not only acts as central metal atom to coordinate with two Schiff base ligands, but also as Lewis acid catalyst to promote the partial decomposition of another salen-type Schiff base ligand. The central ErIII atom adopts an octacoordinate square antiprismatic arrangement with Λ absolute configuration, coordinating with all nitrogen and oxygen atoms of two ligands due to the influence of the strong electron-withdrawing group on the Schiff base ligand. The complex ErL exhibits good SHG and ferroelectric properties. The results provide a simple and effective approach to construct rare earth complexes coordinated with nitrogen and oxygen atoms of salen-type Schiff base ligands with technologically important properties such as SHG activity and ferroelectricity.

Three new compounds, {[Zn(tza)2(H2O)]·H2O}n (1), {[Mn(tza)2(Htza)2]·2H2O}n (2) and [Cd(tza)2]n (3), were obtained by reactions of 1H-Tetrazole-1-acetic (Htza) with corresponding metal salts, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound 1 is three-dimensional (3D) supramolecular structure with line chains. Compound 2 is three-dimensional (3D) supramolecular structure with Mn-carboxylate chains. Compound 3 is a 3D framework with (3,6)-connected ‘ant’ topological network. Furthermore, the photoluminescence of 1 and 3 and the magnetic properties of 2 have also been investigated.

A new type of multifunctional single ionic chiral dysprosium complex (DyL) was obtained by the reaction of Dy(NO3)3 and salen-type Schiff base ligand N,N′-bis(3,5-dichlorosalicylidene)-(1R,2R)-1,2-cyclohexylenediamine. In the synthesis reaction, Dy(III) was found not only to be the central metal to coordinate with two Schiff base ligands, but also the Lewis acid catalyst to promote the partial decomposition of salen-type Schiff base ligand. Complex DyL crystallizes in a chiral and polar space group P21. The central metal Dy(III) adopts eight-coordinated square antiprism geometry with Δ absolute configuration. Complex DyL exhibits good SHG and ferroelectric properties. The single-crystal sample of DyL displays an obvious ferroelectric behavior with a remnant polarization (Pr) of ca. 4.51 μC cm−2 and Ec of ca. 28.11 kV cm−1. The solid luminescent spectrum of DyL presents characteristic emission 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions of Dy(III).

A field experiment was conducted to determine effects of 6 treatments including without fertilization (CK), conventional fertilization (CM), corn straw plus manure (SM), peat plus chicken manure ( PM), mushroom residue plus chicken manure (MM) and high level of chicken manure (HM) on different soil active organic carbon and carbon pool management index. The results showed that fertilization of chicken manure is difficult to prompt activation of soil that contains plenty of fulvic acid, but combined application of different organic fertilizers not only can significantly increase the soil organic matter content, also can balance the proportion between the components of soil humus, improve Hu/Fu. Compared to CK treatment after fertilization, there was a narrow range in HA/TOC, FA/TOC, HM/TOC of HM treatment that was only 4%-8%, but variations of 12%-25% was produced by SM, PM, MM treatment, and its Hu/Fu increased 98% - 292% compared with HM treatment; The quantity of soil microorganisms is enhanced mostly by the treatment of HM, and the increase of bacteria and fungi was the maximum, but the quantity of actinomycetes was increased mostly by MM treatment; high level of chicken manure treatment can increase the risk of nitrate accumulation, but combined application of different organic fertilizers can significantly reduce the nitrate accumulation of vegetables, improving the quality of vegetables. Compared with HM treatment, MM treatment reduces the nitrate content of 45%. Therefore, the results demonstrated that paid attention to the selection of organic fertilizers and its combined application not only would achieve better fertilizing effect, also would better improve the quality of vegetables in organic agricultural production.

Series sensitizers of indoline and triphenylamine as the donor group, quinoxaline and its derivatives as the additional acceptor, different heteroaromatic rings (furan, benzene and selenophene) as the π-conjugated group, 2-cyanoacrylic acid as the acceptor/anchoring which featured on the D–A–π–A architecture have been theoretically designed based on the reported dyes IQ2 and TQ2 used in dye-sensitized solar cells (DSSCs), to shed light on how the additional (auxiliary) acceptor and π spacer influence the performance of the dyes. These enable us to determine master factors influenced the efficiency of DSSCs, such as the light-harvesting efficiency, lifetime of excited state, exciton binding energy, total reorganization energy and electron injection driving force as well as the vertical dipole moment. The theoretical results revealed that compared with dye IQ2, our designed dyes IQS2 and IQS3 displayed much better light harvesting properties and longer first excited lifetime.

A direct dynamics study was carried out at the CCSD(T)/aug-cc-pvtz//B3LYP/6-31G(d,p) level for the multichannel degradation reaction of perfluoropropionic acid (PFPA, CF 3 CF 2 COOH). It is shown that the main pathway of the CF 3 CF 2 COOH degradation reaction can give the main product P2 (CO + CF 3 CO), while the minor product is P1 (C 2 H 4 ). Due to the energetically intermediates and transition states involved in the dominant paths, the reaction is expected to occur rapidly, which is consistent with the experimental data. The present theoretical studies may provide useful information on the issues of the reaction mechanism and product distributions.

A new three-dimensional(3D) coordination polymer, [Cu(atz)(isonic)]n (1) was synthesized hydrothermally from mixed-ligands of Hatz (Hatz = 5-amino-1H-tetrazole) and Hisonic (Hisonic = isonicotinic acid) and corresponding CuII salt. It was characterized by IR spectra, elemental and thermal analysis, structurally and magnetically characterized. In this compound, CuII ions are linked by μ3-atz bridges to give [{Cu2(μ3-atz)2}]2+ cationic layer. The cationic layers are further pillared by isonic ligand and resulted in 3D frameworks with unprecedented topological network. The variable temperature magnetic investigations indicate that compound 1 exhibits typical antiferromagnetic behaviors.

A novel tetranuclear lead-edta compound [Pb4(edta)(H2O)2(N3)4]n (1) (H4edta = ethylenediaminetetraacetic acid) has been synthesized by the reaction of PbF2 with H4edta and NaN3 mixed-ligands under hydrothermal conditions, and was characterized by elemental analysis, thermal analysis, luminescence, powder X-ray diffraction and single-crystal X-ray diffraction. The results of X-ray crystallographic analysis reveal that compound 1 is the first 3D Pb(II)-edta coordination polymer with a high ratio of lead. Remarkably, the edta4− ligand uses all its 10 donor atoms (8O ​+ ​2 ​N) coordinated to Pb(II) ions and formed a 2D layer. The 2D layers are further linked to a complex 3D coordination polymer by the inorganic chain [Pb5(N3)10]n. Time-dependent density functional theory (TDDFT) calculations reveal that the mechanism of the fluorescence emission is dominantly resulted from the ligand-to-metal charge transfer (LMCT) for 1, which is in good agreement with its fluorescence spectra and crystal structure. Optical absorption spectra indicate that 1 has wide optical band-gaps and can be probably used as wide optical band-gap semiconductor material.

Three Pb(II)-edta complexes, [Pb3(edta)(H2O)Cl2]n·(H2O)3n (1), [Pb5(edta)2(H2O)2X2]n·(H2O)2n (X = Cl (2), Br (3)) (H4edta = ethylenediaminetetraacetic acid) have been synthesized by the reaction of PbX2 and H4edta under hydrothermal conditions, and were characterized by elemental analysis, thermal analysis, luminescence, powder X-ray diffraction and single-crystal X-ray diffraction. The results of X-ray crystallographic analysis reveal that these complexes are the first bilayer two-dimensional (2D) Pb-edta coordination polymers with 1D channels. The bilayers of complexes 1, 2 and 3 are linked by [Pb2Cl4], [PbCl2] and [PbBr2] clusters with carboxylate groups respectively. They are 3D supramolecular structures which are resulted from different halogenide anions. The emission spectra of 1–3 are dominated by intense and broad emission bands which are resulted from the [PbX2] clusters. Optical absorption spectra indicate that theses complexes have wide optical band-gaps and can be probably used as wide optical band-gap semiconductor materials.

A new compound of [Cu8(Metz)9](OH)·xH2O (x≈3) (1) (Metz = 5-Methyltetrazole) has been prepared and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The crystal is of hexagonal, space group P63/m with a = b = 13.988(1) A, c = 16.309(2) A, α = β = 90°, γ = 120°, V = 2 763.5 (4) A3, Mr = 1327.13, D c = 1.595 g cm−3, Z = 2, F(000) = 1 316, μ = 3.076 mm−1, the final R = 0.0494 and wR = 0.1532 for 1,731 observed reflections (I > 2σ(I)). In this compound, the [(CuII)2(CuI)6(Metz)9]+ cationic clusters are connected together through CuI cations and Metz ligands and result in a three-dimensional framework. Remarkable, three-dimensional intersecting channels exist in it. The variable temperature magnetic investigations indicate that 1 exhibits typical antiferromagnetic behaviors. N2 gas adsorption measurements at 77 K showed that compound 1 possesses permanent porosities.

A new 3D coordination polymer, Mn2(atz)(isonic)(OH)(Cl)]n (1), was synthesized hydrothermally from mixed-ligands of Hatz (Hatz = 5-amino-tetrazolate) and Hisonic (Hisonic = isonicotinate) and corresponding metal salts. It was characterized by IR spectra, elemental and thermal analysis, single crystal and powder X-ray diffraction. Variable temperature magnetic investigations indicate that compound 1 exhibits typical antiferromagnetic behaviors.

A novel viologen(4,4′-bipyridinium)-based compound FeCl4(4,4′-diethyl-4,4′-bipyH) (1) (bipy = bipyridine), in which 4,4′-diethyl-4,4′-bipyH (MQ +) was generated in situ, is synthesized via the hydrothermal reaction and structurally characterized by single crystal X-ray diffraction. The crystal structure analysis reveals that the title compound features an isolated structure based on 4,4′-diethyl-4,4′-bipyH moieties and an iron atom terminally bound by four chlorine atoms. The 4,4′-diethyl-4,4′-bipyH moieties and (FeCl4)− anions are interconnected by hydrogen bonds to form a 3D supramolecular framework.

One couple of enantiomerically pure chiral Cu II Gd III coordination polymers [Cu(( S , S )-Salcy)Gd(NO 3 ) 3 ·CH 3 OH] n ( 1 ) and [Cu(( R , R )-Salcy)Gd(NO 3 ) 3 ·CH 3 OH] n ( 2 ) [( S , S )-Salcy or ( R , R )-Salcy = ( S , S )- or ( R , R )- N , N ′-(1,2-cyclohexanediylethylene) bis(3-ethoxysalicylideneiminato)dianion], were synthesized and structurally characterized. The self-assembly by intermolecular semicoordination of nitrate to copper(II) formed a one-dimensional zigzag chain structure. Magnetic property studies indicated that 1 and 2 exhibited very strong ferromagnetic interaction ( J = 6.285 and 7.408 cm −1 , respectively) between copper(II) and gadolinium(III) metal centers among the related complexes, although the dihedral angles (8.1° and 8.6°, respectively) of CuO 2 and GdO 2 are a little large.

Two Zn(II) and Cd(II) compounds with the in-situ generated ligand of 5-amino-tetrazolate (atz−) were prepared from the hydrothermal reactions of the corresponding Cd or Zn(II) salts with phenylcarboxylate, and characterized by elemental analysis, IR spectroscopy, and TGA. The results of X-ray crystallographic analysis reveal that compound [Zn2(BZA)(atz)2(OH)]n (1) (BZA=benzoic acid) presents a two-dimensional (2D) “hcb” topological network constructed from the ZnN2O2 tetrahedra. In compound [Cd6(atz)6(PTA)3]n (2) (PTA=terephthalic acid), the identical [Cd3(atz)3)]3+n clusters are connected by atz ligands to generate a 2D cationic layer, and the neighboring cationic layers are pillared by PTA giving birth to 3D network. After simplifying, the complicated 3D network of 2 can be presented as an unprecedented (4, 4, 10)-connected trinodal topology. The formations of the structures show a good example that using the combination of the in-situ generated ligand and other coligand synthetic strategy can construct interesting topological structures. The thermal stabilities and fluorescent properties of the complexes have also been studied.

A new compound of CuCl(QOA)(H2O) (1) [QOA = (8-quinolinyloxy)acetate] has been prepared and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The crystal is of orthorhombic, space group P212121 with a = 5.364(1) A, b = 13.876(3) A, c = 15.435(3) A, V = 1,148.8(4) A3, Mr = 319.19, Dc = 1.846 g cm−3, Z = 4, F(000) = 644, μ = 2.138 mm−1, flack parameter = 0.00(17), the final R = 0.0311 and wR = 0.0646 for 2,179 observed reflections (I > 2σ(I)). Compound 1 consists of one-dimensional helical chains deriving from CuCl(QOA)(H2O) units linked by hydrogen bonds and further extend into a 3D supramolecular structure through Van der Waals interactions, and it exhibits strong luminescent emission at room temperature.

A new Mn(II) complex, [Mn2(edta)(H2O)]n·nH2O (1) (H4edta = ethylenediaminetetraacetic acid) has been synthesized by the reaction of MnCl2·4H2O and H4edta under hydrothermal conditions, and was characterized by single-crystal X-ray diffraction study, variable temperature (1.8–300 K) magnetic measurement, and thermal gravity analysis. The result of X-ray crystallographic analysis reveals that complex 1 is the first two-dimensional (2D) Mn-edta coordination polymer with a grid-like (4,4)-topology, which is built from Mn-carboxylate chains and entirely deprotonated edta4− ligands with a maximum denticity. The variable temperature magnetic data indicate that complex 1 exhibits strong antiferromagnetic couplings.

A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Tb0.5(C6NO2H5)3(H2O)2]2n·(H3O)4n(ZnCl5)n(ZnCl4)2n (1) is synthesized. It has a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that it displays interesting emissions in the violet, blue, green, and yellow regions.

In this paper, maleopimaric acid anhydride (MPA) has been synthesized by the Diels-Alder addition reaction between abietic acid and maleic anhydride. Single crystal X-ray diffraction analysis reveals that MPA crystallizes in the polar space groupP21and contains one MPA and one DMF (Dimethylformamide) molecule in the asymmetric unit. MPA is firstly found to be a new type of low-molecular-mass organic ferroelectric with the saturation spontaneous polarization (Ps) about 60.0-61.6μC·cm-2for single crystal samples, which is close to that of typical inorganic ferroelectric materials. MPA·DMF also shows second-order NLO property, with the second harmonic generation (SHG) responses approximately 0.5 times that of urea.

Two nickel coordination compounds with m-aminophenol-N,N,O-triacetic acid (H3L), [Ni(L)·(H2O)3]2·Ni(H2O)6·4.3H2O (1), and [Ni(L)·H2O]2·Ni(H2O)6 (2), were obtained under similar reaction conditions but at different synthesis temperature. Single crystal X-ray diffraction analysis reveals that both coordination compounds exhibit discrete dimeric entity structures and contain hexaaquanickel cations acting as counter-ions. Unit cell data for (1): triclinic, space group P-1, a = 7.9977(16), b = 10.475(2), c = 12.952(3) A and α = 107.36(3), β = 99.66(3), γ = 96.15(3)°; and for (2): monoclinic, space group P21/c, a = 13.524(3), b = 8.5703(17), c = 13.820(3) A and β = 95.25(3)°. In (1), O–H⋯O hydrogen bonds link the complex anions into a dimeric unit. But in (2), the dimeric unit is generated from two Ni centers bridged by two ligands. Extensive hydrogen bond interactions exist in both coordination compounds, and connect the complex anions, hexaaquanickel cations and/or water molecules, resulting in three-dimensional supramolecular structures. The compounds also have been characterized by elemental analysis, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FT-IR and UV–Vis spectra. More coordinated water molecules of metal ion are substituted by N and/or O donors of ligand at higher reaction temperature.

Two new Mn(II) coordination polymers, [Mn15(atz)18(μ3-OH)4(μ3-SO4)4]n·9nH2O (1) and [Mn8(atz)4(μ-OH)4(μ4-SO4)4(H2O)4]n·nH2O (2) (atz = 5-aminotetrazolate), have been prepared under similar hydrothermal conditions except the difference of the source of the atz ligand. They were characterized by single-crystal X-ray diffraction studies, variable temperature (1.8−300 K) magnetic measurements, and thermal gravity analysis. The results of X-ray crystallographic analysis reveal that compound 1 is a 3D coordination polymer with a (3,4)-connected (83)4(86)3 topology, which is built from trinuclear [Mn3(μ3-SO4)(μ3-OH)] clusters and bridging mononuclear Mn centers. In compound 2, it contains a 3D inorganic cationic [Mn8(μ3-OH)4(μ4-SO4)4]n4+ network with an unprecedented (4,6)-connected topological net, the Schlafli symbol of which is (33·82·9)2(36·84·95). The inorganic cationic net is templated by the atz ligands to form a microporous framework with hydrophilic channels. The variable temperature magnetic data indic...

The first example of isonicotinic acid compounds with infinite mercury halide chains, [HgCl2(C6NO2H5)]nn[HgCl2]n(C6NO2H5) (1), was synthesized through hydrothermal reactions and structurally characterized by X-ray single crystal diffraction. Compound 1 features a one-dimensional (1-D) motif, based on infinite 1-D [HgCl2(C6NO2H5)]n chains, neutral HgCl2 moieties and isolated isonicotinic acid molecules. The [HgCl2(C6NO2H5)]n chains, HgCl2 moieties and isonicotinic acid molecules are interlinked by hydrogen bonds and π-π interactions to give a two-dimensional supramolecular layer. Photoluminescent investigation reveals that the title compound exhibits a strong emission in blue region. The emission band is identified as the π -π* transitions of the isonicotinic acid moieties.

A new coordination polymer, [Cd4(atz)6(PTA)]n has been firstly synthesized by employing mixed-ligand of terephthalic acid (PTA) with the in-situ generated ligand of 5-amino-tetrazolate (atz−). Compound 1 represents a 3D microporous framework constructed from Cd-tetrazolate subunits and the subunits are bridged by PTA and atz ligands. When the subunit was collided into node, compound 1 possesses an unprecedented 3, 9-connected topological network. Furthermore, the investigations of thermal stability and luminescent property of complex 1 indicate that compound 1 may be an excellent candidate for potential blue-light emitting material.

Hydrothermal reaction of TeO2, V2O5, K2C2O4, H2C2O4 in water yielded a novel vanadium tellurite, K3[(VVO4)(VIVO)4(TeO3)4]·4H2O. The compound exhibits ∞2[V4Te4O18]4− puckered anionic layers that are...

The title complex, (N,N′-dimethyl-4,4′-bipyridinium)[Cd2(μ 2-Cl)4Cl2]n (1), in which the N,N′-dimethyl-4,4′-bipyridinium was generated in situ, was synthesized via hydrothermal reaction. X-Ray diffraction analysis revealed that the structure of 1 consisted of MV 2+ (MV 2+ = N,N′-dimethyl-4,4′-bipyridinium) cationic moieties and infinite [Cd2(μ 2-Cl)4Cl2]n anionic chains. The cadmium atom was bound by one terminal chlorine atom and four μ 2-bridging chlorine atoms, yielding a slightly distorted triangular bipyramid. Photoluminescent investigation revealed that the complex displayed an emission in greenish blue region.

A novel trimetallic–isonicotinic acid complex [Zn0.5(H2O)]{(Hg2Cl5)[Eu(C6NO2H4)3(H2O)2]}(HgCl2)·H2O (1) has been synthesised and structurally characterised by single-crystal X-ray diffraction. Complex 1 features a novel 2-D {(Hg2Cl5)[Eu(C6NO2H4)3(H2O)2]} layer constructed from [Eu(C6NO2H4)3(H2O)2] chains interconnected by Hg2Cl5- linkers. The 2-D {(Hg2Cl5)[Eu(C6NO2H4)3(H2O)2]} layers are held together via hydrogen bonds and π–π interactions to yield a 3-D supramolecular framework with the lattice water molecules, the mercury chloride and the hydrated zinc ions located in the cavities.

Five Cd(II) coordination polymers with the in situ generated ligand 5-amino-tetrazolate (atz−) were prepared from the hydrothermal reactions of the corresponding Cd(II) salts, and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA) and single crystal X-ray diffraction. The results of X-ray crystallographic analysis revealed that compounds {[Cd5(atz)9]Cl}n·2nH2O (1) and {[Cd5(atz)9](SO4)0.5}n·2nH2O (3) are isostructural with the perfect Kagome layers bridged by [Cd2(μ4-atz)3] clusters to generate a three-dimensional (3D) rare lon (topological type symbol) topological network with a vertex symbol of 66. Its hexagonal channels are filled by Cl− or SO42− anions and water molecules. Compound [Cd5(atz)8(μ2-Cl)2]n·3nH2O (2) contains three different kinds of bridging modes of the atz− anion and is an intricate 3D polymer. It possesses a 5,6-connected btv topology with a vertex symbol of (47·62·8)2(410·65), which is rarely observed but only predicted by O’Keeffe in theory in coor...

A bimetallic 4f–3d tetranuclear complex {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} · 2H2O · 2Cl (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characterized by a tetranuclear Gd2Zn2 structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. The tetranuclear species of {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} link to isolated chlorine ions and water molecules via π⋯π interactions and hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title complex displays an emission in ultraviolet region. The solid-state diffuse reflectance spectra of 1 reveal the presence of a sharp optical gap of 3.66 eV.

Three new metal–organic frameworks, [Zn(atz)(nic)]n(1), [Zn(atz)(isonic)]n·nHisonic(2) and [Cd(atz)(isonic)]n(3) (Hnic=nicotinic acid, Hisonic=isonicotinic acid), have been firstly synthesized by employing mixed-ligand of pyridinecarboxylate with the in situ generated ligand of 5-amino-tetrazolate(atz−), and characterized by elemental analysis, IR spectroscopy, TGA and single crystal X-ray diffraction. The results revealed that 1 presents a two-dimensional (2D) “sql” topological network constructed from the linear chain subunit of Zn(nic)2 and atz− ligand. A remarkable feature of 2 is a 2-fold interpenetrated diamondoid network with free Hisonic molecules locating in the channels formed by the zigzag chain subunits of Zn(isonic)2. Complex 3 is a 3D non-interpenetrated pillared framework constructed from the double chain subunits of Cd–COO−–Cd. It possesses a rarely observed (4,6)-connected “fsc” topology. The thermal stabilities and fluorescent properties of the complexes were investigated. All of these complexes exhibited intense fluorescent emissions in the solid state at room temperature.

Two 3d/5d–4f metal complexes [DyL3(H2O)2]n(1.5nHgCl4) · 2nH2O (1) and [ EuL ′ 3 ( H 2 O ) 2 ] n (1.5nZnCl4) · nH2O (2), where L and L′ are isonicotinic acid and nicotinic acid, respectively, have been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffractions. Both complexes are characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that complex 1 displays emissions in violet, blue and yellow regions, and the violet emission is stronger than the blue and yellow ones. Complex 2 displays emissions in orange and red regions, and the emission are attributed to the characteristic emissions of 5D0 → 7FJ (J = 0, 1, 2, 3, 4) of Eu3+ ions. Optical absorption spectra reveal the presence of an optical gap of 3.31 and 3.86 eV for 1 and 2, respectively. The magnetic properties show that complex 1 exhibits antiferromagnetic-like interactions.

A 1-D metal-isonicotinato inorganic–organic hybrid complex [Gd(C6NO2H5)3(H2O)2]2 n · (nH5O2)(nZnCl5)(2nZnCl4) · (2nH2O) (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is a 1-D polycationic chain-like structure with unprecedented . Optical absorption spectra of 1 reveal the presence of an optical gap of 3.35 eV. Photoluminescence investigations reveal that the complex 2 display a strong blue-light fluorescent emission band.

A new heterometallic 4 f -3 d complex [Y(C 6 NO 2 H 5 ) 3 (H 2 O) 2 ] n (1.5 n ZnCl 4 ). n H 2 O( 1 ), was synthesized via a hydrothermal reaction and structurally characterized. Complex 1 crystallized in the monoclinic system with space group P 2 1 / c : a =0.94847(9) nm, b =2.0947(2) nm, c =1.6001(2) nm, β=104.467(2)°, V -3.0781(5) nm 3 , M r =823.04, D c =1.776 g/cm 3 , S =1.009, μ(Mo K α)=3.603 mm −1 , F (000)=1632, R =0.0787, and wR =0.2273. Complex 1 , with four formula units in a cell, was characteristic of a one-dimensional polycationic chain-like structure. Photolumincscent investigation showed that the title complex displayed a strong emission in the blue region, which was attributed to the intraligand π-π * transition of the nicotinic ligands. Optical absorption spectrum of complex 1 revealed the presence of a wide optical bandgap of 4.17 eV.

A novel heterometallic metal-isonicotinic acid inorganic-organic hybrid complex [Zn0.5(H2O)]{(Hg2Cl5)- [Er(C6NO2H4)3(H2O)2]}(HgCl2)·0.5CH3OH·0.5H2O (1) has been successfully synthesized via a hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the space group C2/c of the monoclinic system with eight formula units in a cell: a=34.165(4) A, b=9.4692(8) A, c=24.575(3) A, β =115.090(5)°, V=7200(1) A3, C18.50H21Cl7ErHg3N3O10Zn0.50, Mr=1495.25, Dc=2.759 g/cm3, T=293(2) K, µ(Mo Kα) =15.954 mm−1, F(000) =5400 and R1/wR2=0.0561/0.0909 for 3157 observed reflections [I>2δ(I)] and 6468 unique reflections. Complex 1 is characteristic of a novel 2D {(Hg2Cl5)[Er(C6NO2H4)3(H2O)2]} layered structure constructed from the [Er(C6NO2H4)3(H2O)2] chains interconnected by the Hg2Cl5− linkers. The 2D {(Hg2Cl5)[Er(C6NO2H4)3(H2O)2]} layers, mercury chloride and the lattice water molecules are held together via hydrogen bonds to form a three-dimensional framework with the methanol molecules and the hydrated zinc ions located in the cavities. The magnetic properties show that complex 1 exhibits antiferromagnetic-like interactions.

A novel bimetallic 4f–3d complex [Er(C 6 H 5 NO 2 ) 3 (H 2 O) 2 ] n (1.5 n ZnCl 4 ) · (2 n H 2 O) ( 1 ) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characteristic of a novel one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in green and red regions. The luminescence spectra show that the green emission is stronger than the red emission. The green and red emission bands are attributed to the characteristic emissions of 4 F 7/2 , 2 H 11/2 , 4 S 3/2 , 4 F 9/2 → 4 I 15/2 of Er 3+ ions. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.85 eV.