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Five new organic–inorganic hybrid compounds based on [P2W18O62]6− (abbreviated as {P2W18}) and several types of transition metal complexes (TMCs) have been synthesized and characterized by IR, UV-Vis, XRD, cyclic voltammetry measurements and single crystal X-ray diffraction analysis. [Cu(phen)2][Cu(phen)(H2O)3][Cu(phen)2(H2O)][P2W18O62]·8H2O (1) (phen = 1,10-phenanthroline) is a {P2W18} bi-supported complex of phen, while [Cu(2,2′-bpy)(H2O)2]2[Cu(2,2′-bpy)2][P2W18O62]·3.5H2O (2) (2,2′-bpy = 2,2′-bipyridine) is a 1-D chain structure formed by {P2W18} and copper complexes of 2,2′-bpy. [Ag(2,2′-bpy)2]5[HP2W18O62]·H2O (3), [Ag(2,2′-bpy)(H2O)]2[Ag(2,2′-bpy)]2[Ag2(2,2′-bpy)3][P2W18O62] (4), and [Ag(2,2′-bpy)(H2O)]3[Ag2(2,2′-bpy)3][Ag(2,2′-bpy)][P2W18O62]·H2O (5) are constructed from {P2W18} and silver complexes of 2,2′-bpy. Compounds 4 and 5 are novel dimers of {P2W18} joined by silver complexes, while compound 3 contains two different kinds of silver complexes, forming a novel supramolecular structure. Each of the five compounds is formed by {P2W18} and more than one type of TMC. The formation mechanism of these compounds has been carefully discussed. In addition, we also synthesized two supramolecular structures based on {P2W18} and organic moieties: [H6P2W18O62](phen)5.5 (6) and [H6P2W18O62](phen)3·43H2O (7). The catalytic properties of these compounds were also tested. [ABSTRACT FROM AUTHOR]

Abstract: Protein tyrosine phosphatase 1B (PTP1B) is a key factor in the negative regulation of insulin pathway and a promising target for treatment of diabetes and obesity. Herein, the sapogenin 2b, prepared from the natural triterpene saponin 1b, was modified at 3-position to establish the dammarane derivatives library via esterification, oxidation and reductive amination reaction and evaluated as PTP1B inhibitors. 3-O-para-Carboxylphenyl substituted derivative 5b was found with the best in vitro inhibition activity to protein tyrosine phosphatase 1B (IC50 =0.27μM), where 3-O-meta-carboxylphenyl substituted 5a exhibited the best selectivity (nearly fivefolds) between PTP1B and T-cell protein tyrosine phosphatase. [Copyright &y& Elsevier]

Abstract: Three new molybdophosphates, [Co(dien)2]·(H3dien)6·{[CoMo12O24(OH)6(HPO4)2(PO4)6][Co(Hdien)]2[CoMo12O24(OH)6(PO4)8]}·(dien)·4H3O·5H2O (1), (H3dien)4[MMo12O24(OH)6(HPO4)4(PO4)4]·10H2O [M=Co for (2), Ni for (3); dien=diethylenetriamine], have been synthesized by employing hydrothermal method and characterized by single crystal X-ray diffraction. Compound 1 is built up of Co[P4Mo6]2 units as the structural motif covalently linked by [Co(Hdien)] complex subunits to yield an unusual 1-D chain. Compounds 2 and 3 are isomorphic and both display covalent discrete M[P4Mo6]2 cluster structures which are linked by the hydrogen bonds to form 3-D supramolecular networks. Both 1 and 2 display antiferromagnetic interaction and these three compounds all exhibit intensive photoluminescence. [Copyright &y& Elsevier]

Abstract: The hydrothermal reactions of K3[M(C2O4)3] (M=Co, Fe) and imidazole (im) molecule result in the syntheses of two oxalate-bridged transition-metal supramolecular polymers: [Co(im)2(C2O4)] 1 and [Fe2(im)4(C2O4)2] 2. Both exhibit the one-dimensional (1D) zigzag chain structures with the tetradentate oxalato bridges and ancillary im molecules, and are further propagated into a 3D supramolecular network via the interchain weak N–H⋯O hydrogen bonds. The TG behaviors of both are studied and thermally stable up to ca. 180 and 270°, respectively. The third-order non-linear optical properties of both were also studied, and both exhibit the reverse saturable absorption and self-defocusing performance with the γ values of 1.55×10−31 esu for 1 and 1.02×10−31 esu for 2, respectively. [Copyright &y& Elsevier]

Abstract: Two new interesting polyoxometalate derivatives 1 and 2 constructed of modified metal–oxo cluster ions carrying positive and negative changes, respectively, was hydrothermally prepared and structurally characterized by IR, ESR, XPS, elemental analysis and X-ray crystallography. The result of structure determination shows that compound 1 and 2 are isostructural and both contain polyoxocation and polyoxoanion, and both cation and anion are built on mixed Mo–V tetra-capped pseudo-Keggin units with P centre, [Mo8V8O40(PO4)]n-, bonded to four or two [Ni(2,2′-bipy)2H2O]2+ complexes, respectively, via terminal oxygen of the capping V atoms. Magnetism measurement indicates that there exists antiferromagnetic interaction in complex 1 and 2. [Copyright &y& Elsevier]

The novel polyoxovanadate containing antimony [(C2N2H10)2β-{SbIII8VIV14O42(H2O)}](C2N2H8) · 4H2O has been synthesized from a mixture of VOSO4, Sb2O3, en and H2O under hydrothermal conditions. The spherical [β-{SbIII8VIV14O42(H2O)}]4− clusters form a one-dimensional double-chain structure with non-bonding Sb ⋯ O contacts. [Copyright &y& Elsevier]

A novel cerium–adipate coordination polymer [Ce2(ad)3(H2O)2]n(1) has been hydrothermally synthesized and structurally characterized, which possesses three-dimensional network structure constructed from infinite chains of edge-sharing CeO8(H2O) polyhedron and long carbon chains. Each cerium cation binds to nine oxygen atoms belonging to six adipates and one water molecule, the adjacent cerium atoms are linked together through chelating-bridging and bidentate bridging carboxylates to form infinite polyhedron chains along [1 0 0] direction. The starlike distribution of six μ4-adipates around the central cerium generates a complicated network, which is thermally stable without any collapse even though no any guest molecules reside in the large channels. [Copyright &y& Elsevier]

The compound [Cu(en)2]1.5[H3As6V15O42(H2O)] · 3H2O 1 (en=ethylenediamine) has been synthesized and characterized by elemental analysis, IR spectrum and single crystal X-ray diffraction analysis. Crystal structure analysis reveals that compound 1 is not only the first example of one-dimensional sinusoidal chain structure constructed from polyoxometalates and coordination complex fragments but also the first example of one-dimensional chain of polyoxometalates where clusters are connected by one coordination complex fragment and two coordination complex fragments alternatively. [Copyright &y& Elsevier]

The compound [Zn(H2O)4]2[H2As6V15O42(H2O)]·2H2O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) A˚, c=33.970(7) A˚, γ=120°, V=4278.8(12) A˚3, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H2As6V15O42(H2O)]4− anions and [Zn(H2O)4]2+ cations linked through hydrogen bonds into a network. The [H2As6V15O42(H2O)]6− cluster consists of 15 VO5 square pyramids linked by three As2O5 handle-like units. [Copyright &y& Elsevier]

A novel one-dimensional chain coordination polymer [Cu6(CN)6(phen)4]n 1 was synthesized from the simple hydrothermal reaction of Cu(CH3COO)2·H2O, K3[Fe(CN)6] and phen·H2O. With phen, CuCN exhibits a novel B–C–B–C chain array, namely the infinite chain is propagated via alternately three-coordinate (B) and four-coordinate (C) sites of monovalent Cu ions. It should also be noticed that the compound is the first example where the parent chain not only exhibits the [Cu(phen)]+ side arm, but also is directly bound to the chelate ligand. Moreover, the third-order non-linear optical property of compound 1 was also investigated and it shows the reverse saturable absorption and self-focusing performance. [Copyright &y& Elsevier]

The compound (enH2)3.5[As8V14O42(PO4)]·2H2O 1 (en=ethylenediamine) has been synthesized and characterized by means of elemental analysis, IR spectrum, ESR spectrum, XPS spectrum, TG analysis and single crystal X-ray diffraction analysis. The compound 1 crystallizes in monoclinic system, space group C2/c, a=44.280(9) A˚, b=11.963(2) A˚, c=20.939(4) A˚, β=105.59(3), V=10683(4) A˚3, Z=8 and R1(wR2)=0.0398(0.0885). The compound 1 is constructed from [As8V14O42(PO4)]7− anions and H2en cations linked through hydrogen bonds into a network. The [As8V14O42(PO4)]7− cluster consists of 14 VO5 square pyramids linked by 4 As2O5 handle-like units, and includes at its center an ordered PO43− anion. [Copyright &y& Elsevier]

The compound (enH2)3.5[As8V14O42(PO4)]·2H2O 1 (en=ethylenediamine) has been synthesized and characterized by means of elemental analysis, IR spectrum, ESR spectrum, XPS spectrum, TG analysis and single crystal X-ray diffraction analysis. The compound 1 crystallizes in monoclinic system, space group C2/c, a=44.280(9) A˚, b=11.963(2) A˚, c=20.939(4) A˚, β=105.59(3), V=10683(4) A˚3, Z=8 and R1(wR2)=0.0398(0.0885). The compound 1 is constructed from [As8V14O42(PO4)]7− anions and H2en cations linked through hydrogen bonds into a network. The [As8V14O42(PO4)]7− cluster consists of 14 VO5 square pyramids linked by 4 As2O5 handle-like units, and includes at its center an ordered PO43− anion. [Copyright &y& Elsevier]

The complexes [Co(Him)2(μ4-bta)1/2]n 1 and {[Cu(phen)(μ4-bta)1/2]·H2O}n 2 were hydrothermally synthesized at 160°C and their structures were determined by single-crystal X-ray diffraction. Complex 1 was triclinic, space group P–1, a=7.9294(11) A˚, b=9.621(3) A˚, c=9.6461(16) A˚, α=116.772(19)°, β=96.791(13)°, γ=102.787(19)°, Z=2, V=620.3(2) A˚3, R1=0.0252 and wR2=0.0640 [I>2σ(I)]; complex 2 was monoclinic, space group P21/c, a=7.386(3) A˚, b=12.723(4) A˚, c=15.831(3) A˚, β=102.66(2)°, Z=4, V=1451.5(7) A˚3, R1=0.0389 and wR2=0.1033 [I>2σ(I)]. In both of the structures the metal ions were linked by the μ4-bridging benzene-1,2,4,5-tetracarboxylate ligands, resulting in one-dimensional double-metal chains. The synthesized products were characterized by IR spectroscopy, UV–VIS spectra, inductively coupled plasma (ICP), elemental, thermogravimetric (TGA) and magnetic analyses. [Copyright &y& Elsevier]

By using an organic ligand, a new inorganic–organic hybrid compound of cobalt oxalate-vanadate, {[H2(en)]Co2(ox)(V4O12)}n 1, where en = ethylenediamine, ox = oxalic acid, has been synthesized hydrothermally from V2O5,CoCl2·6H2O,H2C2O4·2H2O and en. Crystal data 1, orthorhombic, Cmcm space group, a=11.624(2), b=9.968(2), c=14.900(3) A˚, R1=0.0298, wR2=0.1172. Compound 1 possesses a three-dimensional open-framework with β-cage and is an antiferromagnetic matter. [Copyright &y& Elsevier]

A novel compound, [Cu(en)2(H2O)]4[Cu(en)2]3.5[PMoVI8VIV6O42Cu(en)(1,10′-phen)]3·14H2O 1 (en = ethylenediamine, phen = phenanthroline), was synthesized hydrothermally (170 °C, 10 days, autogeneous pressure) and characterized by IR, ESR, elemental analyses and X-ray crystallography. The results of structure determination show that compound 1 contains three different structure cluster anions [PMoVI8VIV6O42]7− supporting complex cation [Cu(en)(1,10′-phen)]2+, in which one cluster anion possesses typical bicapped Keggin structure, while other two polyanions only have bicapped quasi-Keggin structures, and [Cu(en)(1,10′-phen)]2+ is linked through oxygen atoms to different V positions of two bicapped quasi-Keggin units. [Copyright &y& Elsevier]

The title compound [CuBr(IN)]n 1 was hydrothermally synthesized from a simple reaction of CuBr2–IN–KBr–NaOH–H2O. X-ray analysis revealed that it is a new example containing extended one-dimensional staircase chain in copper(I) halide family. Its structure can be better described as a three-dimensional supramolecular network assembled via a combination of coordinate–covalent bonds and intermolecular hydrogen bonds. Moreover, compound 1 was characterized by elemental analysis, IR spectrum and TGA analysis. [Copyright &y& Elsevier]

The hydrothermal reaction of CuCl2 · 2H2O, Na2MoO4 · 2H2O, NH4VO3, ethylenediamine (en) and H3PO4 yields a novel two-dimensional open-framework material. The extended structure consists of a network of {PMo8V6O42 [Cu(en)2]}5− cages, with each cage connected to three other neighboring units via [Cu(en)2]2+ bridging groups. [Copyright &y& Elsevier]

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 Å3 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. [ABSTRACT FROM AUTHOR]

Simple room-temperature self-assemblies between Cd2+ salts, SCN− and bisimidazole molecules at pH = 2 created three new organically templated thiocyanatocadmates [H2(L1)][Cd(SCN)4]·H2O (L1 = 1,4-bis(1H-imidazol-1-yl)benzene) 1, [H2(L2)][Cd(SCN)4] (L2 = 1,3-bis(2-methylimidazol-1-yl)propane) 2, and [H2(L3)][Cd2(SCN)6] (L3 = 1,4-bis(2-methyl-1H-imidazol-1-yl)butane) 3. X-ray single-crystal diffraction analysis reveals that (i) in 1–3, the SCN− groups doubly bridge the Cd2+ centers to form different thiocyanatocadmates: a linear chain in 1; a zigzag chain in 2; and a 2-D layer network (63 net) in 3; and (ii) in 1, via Nbase–H…NSCN interactions, the L1 molecules extend the thiocyanatocadmate chains into a 2-D supramolecular layer, whereas in 2, the zigzag thiocyanatocadmate chains self-assemble into a 3-D supramolecular network via weak S…S interactions. Photoluminescence analysis indicates that the three title compounds all emit light: blue light for 1 and 2 and green light for 3. At low temperatures, the emission positions of the three compounds hardly change, but the emission intensities are largely enhanced. Interestingly, after turning off the UV lamp, 1 and 2 still briefly emit light (ca. 2 s), which means that 1 and 2 possess phosphorescence properties. Phosphorescence lifetimes at 77 K are 1619 ms for 1 and 247 ms for 2. [ABSTRACT FROM AUTHOR]

Abstract By employing the hydrothermal in situ acylation of organic acid with N 2 H 4 , we constructed a new acylhydrazidate-based Zn2+ coordination polymer [Zn 2 (apo) 2 ]·H 2 O (H 2 (apo) = 4,5-diamino-1,2-dihydropyridazine-3,6-diol) 1. Interestingly, besides the acylation of 2,3-pyrazinedicarboxylic acid (pca) with N 2 H 4 , the breaking of partial C-(=)N bonds in the pyrazine ring also occurred, creating a new bridging-type acylhydrazide molecule H 2 (apo). In 1 , the apo2- molecules exhibit a μ 4 coordination mode, linking the tetrahedral Zn2+ centers into a 2-D layer network with a 44 topology. The photoluminescence analysis indicates that the title compound 1 emit the green light with the maximum at 490 nm upon excitation (λ ex = 380 nm, τ = 12.6 μs). Based on the better photoluminescence behavior of 1 , the sensing ability of 1 on nitroaromatic explosives and inorganic anions were investigated. The results suggest that 1 can selectively detect 2,4,6-trinitrophenol (TNP) and Cr 2 O 7 2-. This should be associated with the larger light adsorption at 380 nm for TNP and Cr 2 O 7 2-. The light adsorption at 380 nm for the other nitroaromatic explosives and inorganic anions is weak. Graphical abstract Structure of an apo2--based layered Zn2+ coordination polymer 1 was reported, and the sensing property of 1 on nitroaromatic explosives and inorganic anions were investigated. fx1 Highlights • Structure of acylhydrazide-based Zn2+ coordination polymer was reported. • Acylhydrazide originated from in situ acylation of organic acid with N 2 H 4. • It can selectively sensing 2,4,6-trinitrophenol. • (vi) It can also selectively sensing Cr 2 O 7 2-. [ABSTRACT FROM AUTHOR]

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 Å2). The tetrahenuclear water clusters with a tetrahedral structure are observed in the pores. [ABSTRACT FROM AUTHOR]

Under hydro(solvo)thermal conditions, the reactions between transition-metal salts and tetracarboxylic acid molecules, with the assistance of organic base molecules, created three new coordination polymers, namely [H 2 (bpp)] 2 [Zn 2 (sph) 2 ]·H 2 O (sph = 4,4′-sulfonediphthalate, bpp = 1,3-bis(piperidyl)propane) 1 , [H 2 (bpp)] 2 [Ni 2 (oph) 2 (H 2 O) 2 ]·2H 2 O (oph = 4,4′-oxydiphthalate) 2 and [H 2 (bpe)] 2 [Ni(Hfph) 2 (bpe)] (bpe = 1,2-bis(pyridyl)ethylene; fph = 4,4′-(hexafluoroisopropylidene)diphthalate) 3 . X-ray single-crystal diffraction analysis reveals that (i) in 1 , the diprotonated bpp molecule acts as a templating agent. The quadruple-bridged sph molecules propagate the tetrahedral Zn 2+ ions into a 2-D layer network in 1 , where two types of circle loops are found; (ii) in 2 , the bpp molecule is also diprotonated. The triple-bridged oph molecules extend the octahedrally coordinated Ni 2+ ions into a 2-D layer network, in which a carboxylate-bridged Ni 2+ chain is observed; (iii) in 3 , the non-protonated bpe molecules link the Ni 2+ ions into a 1-D linear chain. The diprotonated bpe molecule acts as the countercation, while the fph molecule serves as the chelating ligand, existing in the form of Hfph 3− ; and (iv) the 2-D layers for 1 and 2 can both be simplified as a (4,4) net. The photoluminescence analysis reveals that 1 emits blue light with a maximum at 415 nm upon excitation at 355 nm. A magnetic property investigation indicates that antiferromagnetic interactions exist between the Ni 2+ ions in 2 . [ABSTRACT FROM AUTHOR]

5-(3',4'-Dicarboxylphenoxy)isophthalic acid (H4L1) and 5-(2',3'-dicarboxylphenoxy)isophthalic acid (H4L2) were reacted with Cd2+ salt with without the assistance of N-donor ligands, creating five 3D CdII coordination polymers [Cd2(L1)(H2O)5]·H2O (1), [Cd2(L1)(bpe)(H2O)] (bpe=1,2-bis(4-pyridyl)ethene; 2), [Cd2(L1)(bpa)(H2O)] (bpa=1,2-bis(4-pyridyl)ethane; 3), [Cd2(L1)(bpp)] (bpp=1,3-bis(4-pyridyl)propane; 4), and [Cd2(L2)(bpp)2(H2O)2]·H2O (5). Crystal-structure analysis reveals 1) in 1, phthalate moieties for L1 link Cd1 centers into a 1D slightly helical chain; Cd2 centers act as bridges, linking 1D helical chains into a 3D network with a (3,5)-connected topology; 2) in 2-4, although Cd2+ centers were further modified by the introduction of organic bases, L1 molecules still link Cd2+ centers into 3D networks, which can all be simplified as pcu topology; 3) in 2-4, phthalate moieties first link Cd2+ centers into an oligomer, in which carboxylate-bridged discrete or rodshaped secondary building units (SBUs) are found (tetranuclear SBU in 2 and 3, rod-shaped SBU in 4); and 4) in 5, L2 molecules link Cd2+ centers into a 2D (4,4) net; introduced bpp molecules serve as pillar linkers, extending Cd2+-L2 layers into a 3D network of 5. The sensing abilities of 2-5 for nitrobenzene (NB) were investigated. Results revealed that they could all serve as fluorescence probes to sense NB at ppm concentrations. [ABSTRACT FROM AUTHOR]

MOFs with adequate free nitrogen sites have potential applications in dye adsorption and formic acid dehydrogenation. Here, we successfully synthesized a novel 3-D MOF 1 ([(CH3)2NH2][Cd(L)DMA]·0.5DMA·1.5H2O) with a special two-fold interpenetrating framework through a simple solvothermal reaction between CdCl2·1.5H2O and a nitrogen-rich triangular tricarboxylate-based linker (H3L, 4,4′,4′′-s-triazine-2,4,6-tribenzoic acid). After removing the guest molecules of dimethylacetamide (DMA) and H2O, including the coordinated DMA from 1 by vacuum activation at 423 K, a compound named 1′ with a formula of [(CH3)2NH2][Cd(L)] and a similar interpenetrating framework structure was obtained. In comparison with compound 1, the total void volume of 1′ is nearly doubled, and thus may provide higher potential for the adsorption of other guest molecules. Notably, the pyridine N atoms located in the middle of the triangular tricarboxylate-based linker are not involved in the coordination with Cd2+, and are all uniformly dispersed throughout the whole framework of the 3-D MOFs. Due to its unique structural features, the 3-D MOF 1′ could effectively adsorb the cationic dye MB+ for recycling purposes. The rapid adsorption rate (0.7 × 10−2 g mg−1 min−1) and the relatively high capacity (900 mg g−1) for MB+ demonstrate the potential of 1′ in dye adsorption. In addition, 1′ may also be used as an effective support to immobilize PdAu NPs via the double-solvent method. The resultant catalyst Pd0.8Au0.2/1′ exhibits decent catalytic activity for the dehydrogenation of formic acid with a TOF value of 1854 h−1 at 333 K. The existence of a large void volume and accessible pyridine N atoms provide a suitable environment for achieving a high dispersion of PdAu NPs, thereby leading to the formation of a catalytically active and stable supported noble-metal NP catalyst for H2 generation from formic acid decomposition. [ABSTRACT FROM AUTHOR]

By employing the hydrothermal in situ acylation of N 2 H 4 with aromatic polycarboxylic acids, three new acylhydrazidate-extended coordination polymers (CPs) [Pb 2 (3-cppth) 2 (phen) 2 ] (3-cppth = 4-(3-carboxyphenoxy)phthalhydrazidate, phen = 1,10-phenanthroline) 1 , [Cd(4-cppth)(bpy)(H 2 O)]·H 2 O (4-cppth = 4-(4-carboxyphenoxy)phthalhydrazidate, bpy = 2,2′-bipyridine) 2 and [Zn(dcpth) 2 ] (dcpth = 4,5-dichlorophthalhydrazidate) 3 were obtained. X-ray single-crystal diffraction analysis revealed that (i) compound 1 possesses a one-dimensional (1-D) double-chain structure. Via the N–H⋯O interactions between the neighboring acylamino groups, two such double chains aggregate together into a 1-D supramolecular chain. The phen molecules are distributed on the outer side of the supramolecular chain, hindering the further extension of the 1-D supramolecular chain; (ii) compound 2 exhibits a 1-D zigzag-type single-chain structure. Via the hydrogen-bonded interactions between the acylamino groups, compound 2 self-assembles into a two-dimensional (2-D) grid-like supramolecular layer network. The π⋯π interactions between the bpy molecules are observed between the supramolecular layers; (iii) in compound 3 , two hydroxylimino groups for the dcpth I molecules link first the Zn 2+ ions into a dimer, which can be viewed as a tetrahedral node. The dcpth II molecules act as the linkers, extending the tetrahedral nodes into another 1-D double-chain structure, different from that of compound 1 . [ABSTRACT FROM AUTHOR]

In this article, two organic bases (dtb ​= ​1,4-di(1H-1,2,4-triazol-1-yl)benzene; mimb ​= ​1,2-bis((2-methyl-1H-imidazole-1-yl)methyl)benzen) were employed to solvethermally react with AgI in an strong acidic environment, creating two new hybrid haloargentates [pbmt] 0.5 [AgI 2 ] 1 (pbmt2+ ​= ​1,1'-(1,4-phenylene)bis(4-methyl-1H-1,2,4-triazol-4-ium)) and [H 2 (mimb)] 0.5 [Ag 2 I 3 ] 2. Note that pbmt2+ in 1 originated from the in situ N-alkylation of dtb with CH 3 OH. X-ray single-crystal diffraction analysis reveals that (i) 1 exhibits 1-D chain structure, which can be described as an infinite extension of AgI 4 tetrahedra via sharing edge; (ii) in 2 , Ag+ and I− aggregate to form a 3-D iodoargentate with open-framework structure. The photoluminescence analysis reveals that at room temperature, 1 emits yellow light, while at low temperature, it just occasionally emits yellow light, and in most cases it emits yellow-green light. Whether at room temperature or low temperature, 2 always emits yellow light. It means that 1 possesses the fluorescent photo(thermo)chromic properties, whereas 2 does not have these properties. The related mechanism was also discussed. Structures of two new azole-based hybrid iodoargentates (1 and 2) are reported. 1 is found to possess fluorescent photo(thermo)chromic properties. [Display omitted] • Azole molecules and their in-situ N-alkylation have employed in the construction of hybrid materials. • The photoluminescence behavior of two hybrids at different excitation wavelengths and low temperature was studied. • Iodoargentate possesses the fluorescent photo(thermo)chromic properties. [ABSTRACT FROM AUTHOR]

Abstract: Three compounds based on polyoxometalate building blocks, [Cu(en)2]{[Cu(en)2]2[MoVI 5MoV 3VIV 8O40(PO4)]}·4H2O (1), [Co(en)2]{[Co(en)2]2[HMoVI 4MoV 4VIV 8O40(PO4)]}·5H2O (2) and [Ni(en)2]{[Ni(en)2]2[MoVI 5MoV 3VIV 8O40(VO4)]}·2H2O (3) (en=ethylenediamine), have been synthesized and characterized by elemental analysis, IR, XPS, XRD, TGA and single-crystal X-ray diffraction analysis. The result of structure determination shows that isomorphic compounds 1, 2 and 3 feature a one-dimensional chain built from the reduced tetra-capped pseudo-Keggin polyoxoanion, which is further interconnected by [M(en)2]2+ (M=Cu, Co and Ni) groups via the terminal oxygen atoms of polyoxoanions. The crystal data for these compounds are the following: 1, monoclinic, space group C2/c, a =26.702(3)Å, b =13.4539(14)Å, c =19.5987(19)Å, β =108.650(2)°, V =6671.0(12)Å3, Z =4; 2, monoclinic, space group C2/c, a =26.244(3)Å, b =13.5070(17)Å, c =19.581(3)Å, β =106.881(2)°, V =6641.8(15)Å3, Z =4; 3, monoclinic, space group C2/c, a =26.2789(15)Å, b =13.5408(6)Å, c =19.6312(9)Å, β =106.2590(10)°, V =6706.1(6)Å3, Z =4. Variable-temperature magnetic susceptibility measurements of compounds 1 and 3 reveal the feature of antiferromagnetic exchange in these compounds. [Copyright &y& Elsevier]

Abstract: Three novel hetero-polyoxovanadates, [Cd(2,2′-bpy)3]{[Cd(dien)]As8V14O42(H2O)} (1, 2,2′-bpy=2,2′-bipyridine, and dien=diethylenetriamine), [Zn(2,2′-bpy)2]2[As8V14O42(H2O)]·H2O (2) and [Ni(en)2]3[As8V14O42(HPO3)]·4H2O (3, en=ethlenediamine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Crystal data: 1 monoclinic, P2(1)/n, , , , , Z=4. 2, orthorhombic, P2(1)2(1)2(1), , , , . 3, triclinic, , , , , , , , . Compounds 1–3 are all made of the {As8V14O42} shells linked by corresponding transition metal complexes into extended structures. Compound 1 and 2 present 1-D wave-like and tubular structures, respectively, while compound 3 exhibits a novel 2-D structure containing interwinding puckery layers. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interaction between VIV cations in 1 and 2. [Copyright &y& Elsevier]

Abstract: Two three-dimensional (3-D) isostructural metal-organic frameworks (M=Ni, Co; btc=1,2,4,5-benzenetetracarboxylate, pyramellitate, ; ox=oxalate, ) have been synthesized hydrothermally and characterized by single-crystal X-ray diffraction. Each 3-D structure is built from the linkage of secondary building units of trinuclear [M3(CO2)3] clusters by a mixed connector of oxalate and pyromellitate. The third-order non-linear optical properties of the title compounds were studied and both exhibit the reverse saturable absorption and self-defocusing performance with the γ value of 5.03×10−30 esu for 1 and 3.04×10−30 esu for 2. [Copyright &y& Elsevier]

A novel cobalt phosphomolybdate: (NH3CH2CH2NH3)(NH3CH2CH2NH2)3Na3[Co4Mo12O24(OH)6(H2O)2 (HPO4)2(PO4)6]·8H2O 1, has been hydrothermally synthesized (200°C, 5 days, autogenously pressure) and characterized by IR, ESR, XPS, elemental analyses and X-ray crystallography. The crystal data: monoclinic space group C2/c, a=12.3281(3) Å, b=21.5729(4) Å, c=26.0242(5) Å, β=99.5401°(3), V=6825(2) Å3, Z=4, R1=0.0346, wR2=0.0650. The structure of compound 1 is based on Co[Mo6P4]2 units connected together via additional Co2+ ions to give a new three-dimensional framework. The interconnected void and channels in the cobalt molybdophosphate frameworks are filled with counter cations and water molecules. The magnetic property of 1 exhibits antiferromagnetic coupling interactions. [Copyright &y& Elsevier]

A novel copper(II) thiocyanate complex [Cu(im)2(NCS)2] 1 (im=imidazole) has been prepared and characterized by spectroscopic analysis and crystallographic method. This supramolecular compound exhibits a three-dimensional solid state structure constituted by N–H⋯S hydrogen bonds and π–π stacking interactions. The compound in DMF solutions has a very strong third-order non-linear optical (NLO) behavior with absorption coefficient and refractive index α2=1.18×10−11 m w−1, n2=−9.00×10−16 m2 w−1, respectively, and third-order NLO susceptibility χ(3) of 7.00×10−10 esu. [Copyright &y& Elsevier]

The new three-dimensional open-framework cobalt(II) molybdenum(VI) phosphate, (C2H9N2)4(C2H10N2)[Co3Mo4P4O28] 1, has been prepared by the reaction of sodium molybdate, phosphoric acid and ethylenediamine with Co2+ salts. The crystal data for 1 are as follows: Tetragonal, space group I4(1)/a, a=17.088(2) A˚, c=10.745(2) A˚ V=3137.7(9) A˚3, Z=4. The structure of 1 is constructed from CoMo2P tetrahedral units connected by CoO4 tetrahedra through sharing corners. The connectivity leads to the formation of intersecting channels in all three crystallographic directions, resembling an aluminosilicate zeolite, and the channels are filled with charge-compensating ethylenediamine ions. [Copyright &y& Elsevier]

A chiral 3-D open-framework coordination polymer [Co3(μ3-OH)(μ5-btc)(μ6-Hbtc)(H2O)3·6H2O]n was successfully obtained from the mixture of Co(CH3COO)2·4H2O, H3btc (where H3btc=benzene-1,2,4-tricarboxylic acid), NaOH and H2O under hydrothermal condition, which contains a novel and unprecedented coordination mode of btc (see Scheme 1Scheme 1Coordination modes of btc in the compounds having been synthesized. I, μ4-btc (in the literature ); II, μ6-btc and III, μ5-btc (see this paper).). [Copyright &y& Elsevier]

By hydrothermal method, a novel supramolecular compound, Co(NIA)2(H2O)4 was synthesized and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffractometer, indicating that it is a novel polyporous supramolecule with molecular ladder hydrogen-bonded chains. TGA curve shows its thermal stability up to 520 °C. [Copyright &y& Elsevier]

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 Å. 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. [ABSTRACT FROM AUTHOR]

2,4,6-Trinitrophenol (TNP), compared with the other nitro compounds, not only has a strong electron-withdrawing ability, but also has a strong light absorption capacity at a large excitation wavelength. Therefore, the fluorescence material with a large excitation wavelength might be a potential probe for the detection of TNP. Here, by employing the in situ acylation of organic acid with N 2 H 4 , two acylhydrazinotetracarboxylate-based coordination polymers [Cd 2 (HL1)(phen) 2 (H 2 O)]·4.5H 2 O (H 5 L1 ​= ​5,5′-(1,4-dioxo-1,2,3,4-tetrahydrophthalazine-6,7-diyl)bis(oxy)diisophthalic acid; phen ​= ​1,10-phenanthroline) 1 and [Mn 2 (HL1)(phen) 2 ]·7H 2 O 2 were obtained. Phen is used to prevent the formation of a dense network and many hydrogen bonds, which might quench any emission of material. As predicted, 1 only possesses a 1-D broad-ribbon structure, whereas 2 just has a 1-D tube-like structure. And both are found to emit the yellow light, corresponding to the charge transfer from benzene ring moiety to acylhydrazine ring moiety. It means that the acylation changes thoroughly the photoluminescence behavior of organic ligand. Based on their good photoluminescence properties, the sensing ability of both towards TNP was investigated. It is turned out that 1 is not an ideal sensor, even though it can also sense TNP. However, 2 can be considered as an excellent sensor for the detection of TNP. The emission of 2 is almost completely quenched by TNP, while only 20% quenching is observed for the potential interfering analyte 4-nitroaniline (4-NA). The related sensing mechanism is discussed in details. Structures of two new coordination polymers based on ligand generated by in situ acylation reaction were reported. Based on the better photoluminescence properties, their selective detection towards TNP was investigated. Image 1 • Structures of two new coordination polymers based on ligand generated by in situ acylation reaction were reported. • Ligand was originated from in situ acylation reaction of organic acid with N 2 H 4. • Selective detection towards 2,4,6–trinitrophenol (TNP) of two coordination polymers was investigated. • The Mn2+ compound shows the better selectivity towards the detection of TNP. [ABSTRACT FROM AUTHOR]

The simple hydrothermal self‐assembly of metal ions, 5,5′‐(4,5‐dicarboxy‐1,2‐phenylene)bis(oxy)diisophthalic acid (L1'), and N2H4·H2O at pH = 8 (adjusted by oxalic acid) created two new acylhydrazinetetracarboxylate‐extended 3‐D Sr2+ and Ba2+ coordination polymers [Sr2(HL1)(H2O)] (H5L1 = 5,5′‐(1,4‐dioxo‐1,2,3,4‐tetrahydrophthalazine‐6,7‐diyl)bis(oxy)diisophthalic acid) 1 and [Ba5(HL1)2(ox)(H2O)2]·6H2O·N2H4 (ox = oxalate) 2. H5L1 originated from the in situ acylation of L1′ with N2H4. X‐ray single‐crystal diffraction analysis reveals that (i) the 3‐D network of 1 is based on a rod‐like secondary building unit (SBU), which can be described as an alternate arrangement of two types of dinuclear Sr‐O clusters; (ii) the 3‐D network of 2 is also based on a rod‐like SBU. The different is that the SBU for 2 can be described as an alternate arrangement of a kind of trinuclear cluster and a kind of tetranuclear cluster. Both 1 and 2 emit blue light. With regard to their good photoluminescence properties, their trinitrophenol (TNP) sensing ability was investigated. The results indicate that both can selectively detect TNP. The quenching constants Ksv are calculated to be 3.21 × 104m–1 for 1 and 2.98 × 104m–1 for 2, respectively. [ABSTRACT FROM AUTHOR]

Under hydro(solvo)thermal conditions, four organic bidentate bridging N,N′-donor ligands 1,3-bis(2-methylimidazol-1-yl)propane (L1), 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl (L2), 1,2-bis(2-methyl-1H-imidazol-1-ylmethyl)benzene (L3) and 5,6,7,8-tetrahydroquinoxaline (L4) were employed to react with CuBr/CuI, generating four 2-D layered copper(i)–polymer coordination polymer materials [Cu2Br2(L1)] 1, [CuI(L2)] 2, [CuI(L3)] 3 and [CuI(L4)0.5] 4. In 1–4, different Cu–X motifs are found: a cubic Cu4Br4 core in 1; a castellated Cu–I single chain in 2; a rhombic Cu2I2 core in 3; and a staircase-like Cu–I double chain in 4. The 2-D layer networks of 1–3 can all be simplified into a simple 44 topology (planar for 1 and 3; wave-like for 2), while the 2-D layer network of 4 has a 63 topology. The photoluminescence behaviors of 1–4 under a UV lamp suggest that 1 and 2 possess fluorescence thermochromism properties. Under the UV lamp, with the decrease in temperature, (i) 1 exhibits a yellow-to-red emission; (ii) 2 exhibits a yellow-to-green emission; (iii) 3 always emits green light; and (iv) 4 never emits light. These are further confirmed by their emission spectra. From 297 K to 77 K, the emission of 1 exhibits a large red shift from 561 nm to 623 nm; the emission of 2 exhibits a large blue shift from 571 nm to 515 nm; only a minor red shift is observed for the emission of 3; and no peaks appear in the emission spectra of 4. The crystal data of 1 and 2 at different temperatures have been collected for revealing the origination of their fluorescence thermochromism properties. Based on the above investigations, the effect of the rigidity/flexibility of the organic ligand on the fluorescence thermochromism properties of copper(i)–polymer coordination polymer materials is discussed. The quantum yields at 297 K and the photoluminescence lifetimes at 297 K and 77 K for 1–3 were also measured for better understanding their photoluminescence properties. [ABSTRACT FROM AUTHOR]

Abstract By employing the solvothermal in situ N -alkylation of organic bases with alcohol molecules, four new organically templated iodometallates as [L1][Ag 2 I 4 ] (L12+ = 1,1,4,4-tetramethyl-1λ4,4λ4-piperazinium) 1 , [L2] 1.5 [AgI 4 ] (L22+ = 1,4-dibenzyl-1λ4,4λ4-diazabicyclo[2.2.2]octanium) 2 , [L2] 1.5 [CuI 4 ] 3 and [L3][CuI 3 ] (L32+ = 4,4′-bis(3-methyl-1H-3λ4-imidazol-1-yl)-1,1′-biphenylium) 4 were obtained. In 1 , the in situ substitution and N-alkylation of 1,4-bis(pyridin-4-ylmethyl)piperazine (L1') with CH 3 OH has occurred, producing L12+. Templated by L12+, Ag+ and I- aggregate into a chained iodoargentate, which can be described as a linear arrangement of AgI 4 tedrahedra by sharing the edges. 2 and 3 are isostructural. In 2 and 3 , the in situ N -alkylation of 1,4-diazabicyclo[2,2,2]octane (L2') with phenylmethanol has occurred, generating L22+. Templated by L22+, Ag+ (or Cu+) and I- aggregate into a mononuclear iodometallate with a tetrahedral structure. In 4 , the in situ N -alkylation of 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl (L3') with CH 3 OH has occurred, creating L32+. Templating by L32+, Cu+ and I- aggregate into a mononuclear iodocuprate(I) with a planar trigonal structure. The photoluminescence analysis reveals that (i) at the room temperature, only 1 emits light (λ em = 550 nm); (ii) at the low temperature, 4 is found to possess the photoluminescence property (λ em = 546 nm at 77 K) with a ms-grade lifetime (τ = 4.915 ms). Graphical abstract By employing solvothermal in situ N -alkylation of organic bases with alcohol molecules, four new organically templated iodometallate(I) were obtained, and their photoluminescence properties were investigated. fx1 Highlights • Four new organically templated iodometallates(I) (M+ = Ag+, Cu+) are reported; • In situ N -alkylation of 1,4-diazabicyclo[2,2,2]octane with phenylmethanol is investigated for the first time; • In situ N -alkylation of 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl with alcohol molecules is investigated for the first time; • Their photoluminescence properties at different temperature are investigated. [ABSTRACT FROM AUTHOR]

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)22− 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. [ABSTRACT FROM AUTHOR]

Through employing the in situ acylation of N 2 H 4 with ODPA (ODPA = 4,4′-oxydiphthalic dianhydride), three diacylhydrazidate-extended coordination polymers, M(ODPTH)(H 2 O) 3 (M = Fe ( 1 ), Co ( 2 ), Ni ( 3 ); ODPTH = 4,4′-oxydiphthalhydrazidate), were obtained under solvothermal conditions. The X-ray single-crystal diffraction analysis reveals that compounds 1 , 2 and 3 are isomorphous and feature 1D double chain structures that are further connected through O–H⋯O hydrogen bonds into 3D supramolecular networks, which are stabilized by two kinds of offset face-to-face π⋯π interactions. All of title compounds were characterized by IR spectroscopy, elemental analysis, X-ray power diffraction and TG analysis. Furthermore, variable-temperature magnetic susceptibilities of compounds 1 , 2 and 3 indicate that there exist antiferromagnetic interactions between Fe(II), Co(II) and Ni(II) ions, respectively. [ABSTRACT FROM AUTHOR]

Through employing the in situ acylation of N 2 H 4 with 2, 3-quinoline dicarboxylic acid, three acylhydrazidate-extended coordination complexes, M(QLH)(H 2 O) 2 Cl (M = Mg ( 1 ) or Mn ( 2 ); QLH = 2, 3-quinolinedicarboxylhydrazidate) and Mn(QLH) 2 (H 2 O) 2 ( 3 ), were obtained under solvothermal conditions. The X-ray single-crystal diffraction analysis reveals that: (i) compounds 1 and 2 feature a dinuclear structure. Via two kinds of O–H⋯O and O–H⋯Cl hydrogen bonds, the discrete dinuclear units of 1 and 2 self-assemble into 3-D supramolecular networks, which are stabilized by the offset face-to-face π···π interactions; (ii) compound 3 features a mononuclear structure, which self-assembles into a 2-D supramolecular network via two types of O–H⋯O and N–H⋯N hydrogen bonds, and the strong face-to-face π···π interactions strengthen the 2D supramolecular layers. All of title compounds were characterized by IR spectroscopy, elemental analysis, power X-ray diffraction and TG analysis. The photoluminescent properties of 1 , 2 and 3 were investigated. Compounds 1 and 3 emitted green light with maxima at 529 nm for 1 ( λ ex = 364 nm), and 498 nm for 3 ( λ ex = 366 nm), while compound 2 emitted purple light with maxima at 381 nm ( λ ex = 338 nm). Furthemore, density functional theory (DFT) calculations were carried out on the excited electronic states of 1 , 2 and 3 in order to further investigate the emission mechanism. Meanwhile, variable-temperature magnetic susceptibilities of 2 and 3 indicated that there existed weak antiferromagnetic interactions between Mn (II) ions. [ABSTRACT FROM AUTHOR]

Under hydrothermal conditions, the simple self-assembly of Ni 2+ , H 2 C 2 O 4 and N 2 H 4 created a new 3-D Ni 2+ coordination polymer, [Ni(C 2 O 4 )(N 2 H 4 )]·H 2 O (C 2 O 4 2− = oxalate, N 2 H 4 = hydrazine) 1 , in which C 2 O 4 2− ligands link Ni 2+ ions into a left-hand helical Ni(C 2 O 4 ) chain, while N 2 H 4 extends the Ni(C 2 O 4 ) chains into a 3-D network with a 10 3 topology. A magnetic susceptibility study indicates that between the neighboring Ni 2+ centers, there exist antiferromagnetic interactions. [ABSTRACT FROM AUTHOR]

The hydro(solvo)thermal reactions of CuI with diverse bisimidazole molecules were investigated, affording five new copper(I) iodides [Cu 4 I 4 (L1) 2 ] (L1=1,3-bis(2-methylimidazol-1-ylmethyl)benzene) 1 , [CuI(L2)] (L2=4,4′-bis(imidazolyl)biphenyl) 2 , [Cu 4 I 4 (L3)] (L3=1,3-bis(2-methylimidazol-1-yl)propane) 3 , [Cu 4 I 4 (L4) 2 ] (L4=1,4-bis(2-ethylimidazol-1-yl)butane) 4, and [Cu 4 I 4 (L5)] (L5=1,4-bis(1-imidazoly)benzene) 5 . X-ray single-crystal diffraction analysis reveals that (i) in 1 , a tetranuclear Cu-I cluster (stepped cubane) is observed, and the L1 molecule only acts as an ancillary ligand; (ii) in 2 , the L2 molecules extend the castellated Cu-I chains into a 2-D layer network with a certain thickness; (iii) in 2-D single-layer network of 3 , a 1-D Cu-I column is found, which can be viewed as a longitudinal packing of stepped Cu 4 I 4 cubanes; (vi) in 4 , the L4 molecules propagate the cubic Cu 4 I 4 cubanes into a 3-D 4-fold interpenetrated network with a cds topology; and (v) in 5 , the L5 molecules link the 1-D Cu-I ribbons into a 2-D single-layer network. The photoluminescence analysis indicates that 1 , 2 and 4 emit light (red light for 1 ; yellow light for 2 and 4 ), while 3 and 5 are not emissive. Their photoluminescence behaviors are confirmed to be related to the Cu···Cu interactions in the molecules. [ABSTRACT FROM AUTHOR]

Based on a strategy of incorporating the SCN − group into the organically templated halocadmate, the reactions of CdCl 2 , SCN − , and bisimidazole molecules in a strong acidic environment at 4 °C were carried out, creating two new organically templated 2-D layered thiocyanato-chlorocadmates [H 2 (L1)][Cd 2 Cl 5 (SCN)] (L1 = bis(1H-imidazole-1-yl)methane) 1 and [H 2 L2] 2 [Cd 5 Cl 12 (SCN) 2 ] (L2 = 1,3-bis(2-ethylimidazol-1-yl)propane) 2 . Both layers are based on a kind of tetranuclear Cd–Cl cluster. Since the employed organic cations are different, the neighboring tetranuclear Cd–Cl clusters are linked together by the different bridges into the 1-D endless chains. In 1 , the Cl − ions act as the bridges, while in 2 , the CdCl 6 units serve as the bridges. Finally, the 1-D Cd–Cl chains are further linked by SCN − into the 2-D layer networks of 1 and 2 . Both layers possess a simple (4,4) topology. Based on the structural characterization of the title compounds, the role of the introduced SCN − group on the organically templated halocadmates is discussed. [ABSTRACT FROM AUTHOR]

Based on an aim of introducing the SCN − or SO 4 2 − group into the organically templated chlorocadmates, a series of room-temperature reactions at pH 2 were performed, creating four new Cd(II) hybrids as [L1] 4 [Cd 4 Cl 6 (SCN) 10 (H 2 O) 2 ] (L1 = 1,1′-dibenzyl-4,4′-bipyridium) 1 , [H 4 L2][CdCl 4 (SCN) 2 ] (L2 = 1,4-bis(4-pyridylmethyl)piperazine) 2 , [HL3] 3 [CdCl 3 ]SO 4 (L3 = 2-amino-6-chloropyridine) 3 , and [HL4] 3 [CdCl 3 ]SO 4 (L4 = 2-amino-6-bromopyridine) 4 . X-ray single-crystal diffraction analysis reveals that (i) templated by L1 2+ , 1 shows a 1-D single-chain structure, which is based on the dinuclear [Cd 2 Cl 3 (SCN) 4 (H 2 O)] 3 − clusters by the μ-1,3-mode SCN − groups; (ii) templated by H 4 L2 4+ , 2 only exhibits a mononuclear structure. However, via the intermolecular weak N pyridine H⋯Cl, N piperazine H⋯Cl and S SCN ⋯S SCN interactions, 2 self-assembles into a 3-D supramolecular network with a (4,6)-connected topology; (iii) 3 and 4 possess the similar structures. Via the N pyridine/amino H⋯O and π⋯π interactions, the introduced SO 4 2 − groups and the organic base molecules aggregate together into a 3-D supramolecular network with the 1-D channels. Within the channel, the Cl − ions triplely bridge the Cd 2+ centers into a 1-D linear [CdCl 3 ] − chain. Based on the structural information and the previous related reports, the role of the introduced SCN − or SO 4 2− group in the hybrid is revealed. SCN − acts as two roles: (i) a linker; (ii) a cutter. Sometimes SO 4 2− serves as a linker, while sometimes SO 4 2− connects with organic base into a supramolecular aggregation, acting as a new templating agent. The photoluminescence analysis reveals that 2 , 3 and 4 emit light with the maxima at 535 nm for 2 ( λ ex = 465 nm), 462 nm for 3 ( λ ex = 428 nm), and 465 nm for 4 ( λ ex = 430 nm), respectively. In particular, the emissions for all are strong, and can be seen under the ultraviolet (UV) lamp. [ABSTRACT FROM AUTHOR]

Based on the hydrothermal in situ acylation reaction of benzene-1,2,4-tricarboxylic acid (btca) with N 2 H 4 ·H 2 O, two containing-4-carboxylphthalhydrazidate Mn 2+ /In 3+ coordination polymers, [Mn(cpth)(phen)] 1 and [In(cpth)(ox) 0.5 (phen)]·H 2 O 2 (cpth = 4-carboxylphthalhydrazidate, phen = 1,10-phenanthroline, ox = oxalate), were obtained and characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. In compound 1 , the cpth ligands exhibit a μ 4 -bridging mode, which link Mn(II) centers into a 2-D layer structure with ancillary phen molecules. In compound 2 , the cpth ligands exhibit a μ 2 -bridging mode, which link In(III) centers into a binuclear unit. Ox ligands act as the second linkers, extending binuclear unit into a 1-D chain with ancillary phen molecules. Via N H⋯O interactions, compound 2 self-assembles into a 2-D supramolecular layer. The magnetic analysis indicates that there exists antiferromagnetic interactions between magnetic centers in compound 1 . The photoluminescence properties of compounds 1 and 2 were also investigated in an aqueous solution. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]