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The ternary combination of CuI, lanthanide cations and electron-deficient viologen based organic tectons led to a donor–acceptor (D–A) hybrid heterostructural framework with a narrow energy gap. Thanks to the electron transfer between inorganic donors (cuprous iodide clusters) and organic acceptors (viologen based tectons), this unique hybrid framework exhibits enhanced photocatalytic activities towards the degradation of rhodamine B (RhB) in comparison with those of lanthanide cations and bulk CuI.

Chiral compounds are known to be important not only because they are the fundamental components of living organisms, but also for their unique chiroptical properties. In recent years, scientists have fabricated several chiral organic supramolecular aggregates by using chiral physical fields, such as vortex flow. Herein, the relationship between dynamic chiroptical properties and rheological nature is discussed, suggesting the shear thinning properties of non-Newtonian fluids might help colloidal particles adopt a chiral arrangement in vortices. Furthermore, the storage modulus of colloids could be increased by adding a linking agent, which successfully kept the dynamic chiroptical properties in the static state. Moreover, the salt effect on the host-guest interaction involved in the colloids was studied, the results suggested a significant enhancement of the transferred dynamic circular dichroism for the achiral guest molecule.

Naphthalenediimides, an attractive class of electron-deficient organic dyes with rich redox and photoredox properties, have been investigated extensively as building blocks for coordination networks or metal–organic frameworks in recent decades. However, most of the available work has focused on d-block metal cations rather than f-block lanthanide ions, whose complexes exhibit a large variability in coordination numbers. In this article, four coordination polymers composed of naphthalenediimides and lanthanide cations, namely catena-poly[[[tris(nitrato-κ2 O,O′)lanthanide]-bis{μ-N,N′-bis[(1-oxidopyridin-1-ium-3-yl)methyl]-1,8:4,5-naphthalenetetracarboxdiimide-κ2 O:O′}-[tris(nitrato-κ2 O,O′)lanthanide]-μ-N,N′-bis[(1-oxidopyridin-1-ium-3-yl)methyl]-1,8:4,5-naphthalenetetracarboxdiimide-κ2 O:O′] methanol disolvate], {[Ln(C26H16N4O4)1.5(NO3)3]·CH3OH} n , with Ln = Eu, 1, Gd, 2, Dy, 3, and Er, 4, have been successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analyses revealed that the four compounds are isomorphic and that each asymmetric unit contains one nine-coordinated Ln centre, one and a half diimide ligands, three nitrate anions and one uncoordinated methanol molecule. In addition, each metal centre is surrounded by nine O atoms in a distorted tricapped trigonal–prismatic geometry. Two centres are bridged by two cis ligands to form a ring, which is further bridged by trans ligands to generate one-dimensional chains. Neighbouring chains are stacked via π–π interactions between pyridine rings to give a two-dimensional structure, which is stabilized by π–π interactions between naphthalene rings, forming the final three-dimensional supermolecular network. Solid-state optical diffuse-reflectance spectral studies indicate that compound 4 is a potential wide band gap semiconductor.

A novel stilbene-based salicylhydrazone compound {systematic name: (E)-4,4′-(ethene-1,2-diyl)bis[(N′E)-N′-(2-hydroxybenzylidene)benzohydrazide] dimethyl sulfoxide disolvate, C30H24N4O4·2C2H6OS or L·2DMSO} was synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction and luminescence spectroscopy. The title compound crystallizes in the monoclinic space group P21/c, with half a symmetry-independent L molecule and one dimethyl sulfoxide (DMSO) solvent molecule in the asymmetric unit. The L molecule adopts an almost planar structure, with a small dihedral angle between the planes of the stilbene and salicylhydrazone groups. There are multiple π–π stacking interactions between adjacent L molecules. The DMSO solvent molecules act as proton donors and acceptors, forming hydrogen bonds of various strengths with the L molecules. In addition, the geometry optimization of a single molecule of L and its luminescence properties either in solution, as a solvated solid or as a desolvated solid were studied. The compound shows an aggregation-induced emission (AIE) effect and exhibits switchable luminescence colouration in the solid state by the simple removal or re-addition of the DMSO solvent.

Naphthalene diimides are attracting considerable interest because of their tunable luminescent properties, which are generally achieved by the incorporation of electron-donating moieties into naphthalene diimides core to form donor-acceptor compounds through covalent bond. However, this method is an elaborate strategy because the separation of byproduct is tedious. Here we report that the luminescent properties of naphthalene diimides can be finely modulated by supramolecular cocrystal formation. Through the donor-acceptor interactions between the electron-deficient N,N′-di-(4-pyridyl)-1,4,5,8-naphthalene diimide (DPNDI) molecules and electron-rich naphthalene derivatives (guest), a series of cocrystal complexes are successfully fabricated. These cocrystal complexes show guest-dependent color-tunable emissions, which originate from the excited state charge transfer interactions between the DPNDI and naphthalene derivatives in the solid state. The present study anticipates providing a new method for the design of various new types of organic luminescent materials.

Naphthalenediimides, a class of organic dyes with an expanded π-electron-deficient plane, have attracted considerable interest because of their photoinduced electron transfer from neutral organic moieties to stable anionic radicals. This makes them excellent candidates for organic linkers in the construction of photochromic coordination polymers. Such a photochromic two-dimensional coordination polymer has been prepared using N,N′-bis(pyridin-4-ylmethyl)naphthalene-1,8:4,5-bis(dicarboximide) (DPMNI). In crystallization tubes, upon slow diffusion of an MeOH solution of cadmium perchlorate into a CHCl3 solution of DPMNI, the complex poly[[bis[μ2-2,7-bis(pyridin-4-ylmethyl)benzo[imn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetrone-κ2 N:N′]bis(perchlorato-κO)cadmium(II)] chloroform tetrasolvate], {[Cd(C26H16N4O4)2(ClO4)2]·4CHCl3} n , (I), was obtained. The asymmetric unit contains one Cd2+ cation, two DPMNI ligands, two coordinated ClO4 − anions and four CHCl3 solvent molecules. Each Cd2+ cation is interconnected by four DPMNI linkers to generate a neutral two-dimensional naphthalenediimide coordination network with all the ClO4 − anions above or below this plane. Strong interlaminar anion–π interactions between the coordinated ClO4 − anions and the imide rings of an adjacent layer lead to a three-dimensional supramolecular structure. Compound (I) exhibits reversible photochromic behaviour and photocontrolled tunable luminescence properties, which may originate from the photoinduced electron-transfer generation of radicals in the DPMNI ligand.

The reaction of CdCl2·2.5H2O with 1,1′-bis(3-carboxybenzyl)-4,4′-bipyridinium dichloride (H2L1·Cl2) or 4,4′-bis[(3-carboxypyridino)methyl]-biphenyl dichloride (H2L2·Cl2) in a dimethylformamide/methanol mixed-solvent system at room temperature, affording the complexes [(CdCl2)3(L1)3]n (1) and {[CdCl2(L2)(H2O)2]·2H2O}n (2). They were characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. Both 1 and 2 exhibit 1D coordination networks, which further stack into a 3D supramolecular structure by hydrogen bonding and π–π interactions. Furthermore, these two complexes exhibit different photochromic behavior in the solid state, which may originate from different charge-distributions of H2L1·Cl2 and H2L2·Cl2 ligands.

Manganese(II) and nickel(II) coordination polymers, [Mn(L)(H2O)2] n (1) and [Ni(L)·14H2O] n (2), have been synthesized from a rigid viologen-based tetracarboxylic acid ligand, 1,1′-bis(3,5-dicarboxyphenyl)-4,4′-bipyridinium dichloride (H4L·2Cl) and the Mn(II)/Ni(II) chlorides. The compounds have been characterized by infrared spectra, elemental analyses, single-crystal and powder X-ray diffraction analyses and thermogravimetric analyses. Compound 1 has a 2D coordination network with uncoordinated carboxyl groups, which further stack into a 3D supramolecular structure by hydrogen-bonding interactions. Compound 2 shows a 3D supramolecular framework with 1D channels along the crystallographic b-axis, formed from zigzag chains through hydrogen-bonding interactions. Both compounds display prominent photochromic and photomagnetic behavior upon light irradiation, suggesting that they may be potential photomagnetic materials.

Naphthalene diimides, which are planar, chemically robust and redox-active, are an attractive class of electron-deficient dyes, which can undergo a single reversible one-electron reduction to form stable radical anions in the presence of electron donors upon irradiation. This makes them excellent candidates for organic linkers in the construction of photochromic coordination polymers. Such a photochromic one-dimensional linear coordination polymer has been prepared using N,N′-bis(3-carboxyphenyl)naphthalene-1,8:4,5-tetracarboximide (H2BBNDI). Crystallization of H2BBNDI with magnesium nitrate in an N,N′-dimethylformamide (DMF)/ethanol/H2O mixed-solvent system under solvothermal conditions afforded the one-dimensional coordination polymer catena-poly[[bis(dimethylformamide-κO)magnesium(II)]-bis[μ-N-(3-carboxylatophenyl)-N′-(3-carboxylphenyl)naphthalene-1,8:4,5-tetracarboximide-κ2 O:O′]], [Mg(C28H13N2O8)2(C3H7NO)2] n . The asymmetric unit contains half of a magnesium cation, one HBBNDI− ligand and one DMF molecule. Two partially deprotonated HBBNDI− ligands bridge two magnesium cations to form a one-dimensional chain. Strong inter-chain π–π interactions between the naphthalene rings of the HBBNDI− ligand and the imide rings of adjacent chains provide a two-dimensional structure. The supramolecular three-dimensional framework is stabilized by π–π interactions between naphthalene rings of neighbouring two-dimensional supramolecular networks. The complex exhibits a reversible photochromic behaviour, which may originate from the photoinduced electron-transfer generation of radicals in the HBBNDI− ligand.

The MnII-based porous metal-organic framework, [Mn3(btca)2(HCOO)(μ3-OH)(H2O)2]·2DMF (1) (H2btca = benzotriazole-5-carboxylate acid), was prepared by the solvothermal reaction of Mn(CH3COO)2·4H2O and H2btca, which was characterized by infrared spectroscopy, thermogravimetric analyses, and X-ray crystallographic study. 1 exhibits 3D framework with 1D rectangle channels constructed by the strip-shaped chains containing [Mn5(μ3-OH)2(btca)4]– pentaclusters subunits. Furthermore, the magnetic measures show that 1 exhibits weak ferromagnetic behavior at low temperature.

The insertion of electron-rich iodoplumbate nanowires and nanolayers into layered electron-deficient metal-viologen frameworks leads to two donor-acceptor hybrid structures, respectively, which exhibit interesting semiconductor behaviors. Due to the bicontinuous donor and acceptor components, both of them exhibit highly efficient photocatalytic degradation activities over organic dyes under visible light irradiation compared to those of other iodoplumbate hybrid materials.

Based on a multi-dentate salicylhydrazide-derived ligand, a Zn-contained metal–organic gel that could stand for months has been prepared. The driving force within the supramolecular assembly was discussed by studying the gelation conditions, optical spectra, dynamic rheology and mass spectra. These studies revealed that both the coordination bonds and hydrogen bonds participate in the supramolecular assembly. In addition, electrostatic force also played as a key role in stabilizing the gel phase. The charge nature of the colloidal particle is negative charged. Consequently, the xerogel shows significant adsorption behavior that favors positively charged dye molecules, such as methyl violet and methylene blue. The title gel exhibits gelation-induced fluorescence enhancement property. When the gel was exposed to ammonia vapor, a gel–solution transition occurred, accompanied by a great weakening of fluorescence. The phase transition and fluorescence switching were found to be reversible for at least seven cycles. The mechanism involved was studied and discussed.

Herein, we report an unprecedented hybrid structure of electron-rich iodoplumbate nanowires precisely inserted into the periodic pores of electron-deficient pyridinium metal-organic frameworks (MOFs). To the best of our knowledge, this is the first example of semiconductive MOFs in situ loaded with inorganic semiconductive nanowires via a simple self-assembly method. Due to the dissimilar semiconductivities between the host and guest components, this hybrid also represents the first bicontinuous donor-acceptor hybrid at the molecular level based on host-guest interactions.

Four metal–organic coordination compounds Zn2(bcbp)Cl4 (1), Zn(bcbp)(PO3F) (2), [CdCl(Hbcbp)(bcbp)]·(ClO4)2 (3), and [Cd2(bcbp)4]·(ClO4)·F3 (4) (H2bcbp·2PF6 = 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) hexafluorophosphate) have been synthesized via a solvothermal method and structurally characterized. Compound 1 is a 1D coordination polymer, while compound 2 shows a 2D + 2D → 3D inclined polycatenation structure. In the case of compound 3, due to the capped chlorine atoms and uncoordinated carboxyl of bcbp ligand, it exhibits a 1D T-shaped coordination configuration. Compound 4 is an unprecedented 13-fold interpenetrating structure with huge diamondoid frameworks. Because of the presence of electron-deficient bipyridinium moieties, the photochromic behaviors of these compounds have also been studied. Interestingly, only compounds 1–3 exhibit color changes under light irradiation. The impact of these anions on the photochromic process is discussed.

Naphthalenediimides, a class of organic dyes with an expanded π-electron-deficient plane, have attracted considerable interest because of their photoinduced electron transfer from neutral organic moieties to stable anionic radicals. This makes them excellent candidates for organic linkers in the construction of photochromic coordination polymers. Such a photochromic two-dimensional coordination polymer has been prepared using N,N'-bis(pyridin-4-ylmethyl)naphthalene-1,8:4,5-bis(dicarboximide) (DPMNI). In crystallization tubes, upon slow diffusion of an MeOH solution of cadmium perchlorate into a CHCl

A stable three-dimensional coordination polymer, [Eu3(bcbp)3(NO3)7(OH)2]n (1) (H2bcbp·2Cl = 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) dichloride), was prepared by the solvothermal reaction of Eu(NO3)3·6H2O and H2bcbp·2Cl in methanol, which was characterized by infrared spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analyses. In the solid state, 1 consists of an unusual trinuclear Eu(III) unit (Eu3(CO2)6(NO3)7(OH), Eu3–SBU), which further connects to six neighboring ones through six bcbp ligands to form a three-dimensional network. As expected, 1 exhibits a strong red-light emission at ambient temperature. Due to the presence of the electron-deficient bipyridinium moiety in the conjugation, this emission is selectively quenched by electron-rich organic amine compounds with high sensitivity and exhibits a prominent visual color change.

Metal-ion-directed assembly of naphthalene diimide tectons cooperatively enhanced by anion-π interactions of giant anions, PMo12O40(3-), leads to a novel organic-inorganic hybrid with ultrafast-responsive photochromic properties, which is attributed to the polyoxometalate-sensitized photo-induced radical generation of naphthalene diimide units.

The title coordination polymer, {[Cd2(CH2N5)(C6H4NO2)Cl(OH)]·0.14H2O}n, (I), was synthesized by the reaction of cadmium acetate andN-(1H-tetrazol-5-yl)isonicotinamide in aqueous ammonia, using hydrochloric acid to adjust the pH. Under hydrothermal conditions,N-(1H-tetrazol-5-yl)isonicotinamide slowly hydrolyzes to form isonicotinic acid (Hisonic) and 5-aminotetrazole (Hatz). The deprotonated form of isonicotinic acid (denoted isonic) acts as a bridging ligand in the structure. The polymer crystallizes in the monoclinic space groupC2/m. In the structure, there is one Cd3(μ3-OH) unit ofCssymmetry, with one of the CdIIatoms and the O and H atoms located on a mirror plane. The other crystallographically independent CdIIcation is located on an inversion centre. Each edge of the Cd3(μ3-OH) isosceles triangle is bridged by an atz ligand in a μ1,2or μ2,3/μ3,4mode. The Cd3(μ3-OH) units are laced around with a belt of chloride ligands. The belts are further connected into undulating layersviaweak inter-belt Cd—Cl bonds. The two organic ligands reside across mirror planes. The construction of a three-dimensional framework is completed by the pillaring isonic ligand. Water molecules partially occupy the voids of the framework.

Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL-responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL-induced enantioselective synthesis. By irradiation with either left-handed or right-handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left-handed CPL resulted in crystals with a left-handed helical structure, and right-handed CPL led to crystals with a right-handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers.

Shape-anisotropic nanomaterials with uniform lengths and widths have attracted much interest but few of them are involved in self-assembled manganese complexes. The combination of two redox-active acylthiosemicarbazide ligands with Mn3+ cations leads to two discrete polynuclear Mn nanorods, pentanuclear [Mn5(L3)6][Mn0.7(DMF)1.4(H2O)2.8] (1a) and trinuclear Mn3(L4)3·2DMF (2), whose L3 and L4 represent N-(5-(2-hydroxyphenyl)-1,3,4-oxadiazol-2-yl)benzamide and N-(5-(2-hydroxyphenyl)-1,3,4-oxadiazol-2-yl)-propionamide, respectively, which are in situ synthesized from their acylthiosemicarbazide derivatives in the presence of Mn3+ cations, while the latter are reduced into divalent ones in rod-like moieties. For each pentanuclear anion in 1a, the charge is balanced by a solvated trivalent manganese cation, which can be replaced by two tetramethylammonium cations to yield pure valence compound 1b. Moreover, the magnetic studies reveal all of them possess antiferromagnetic properties.

Five heterometallic complexes were prepared in aqueous solution at 3–5 °C and characterized by elemental analyses, inductively coupled plasma analysis, IR spectra, UV–Vis spectra, powder X-ray diffraction and X-ray single-crystal diffraction. Complex 1–5 all contain 4d–4f super tetrahedron cluster anions, which are constructed by LnIII ions (Ln = NdIII, PrIII), [MoO4]2− and [Mo7O24]6− anions. Differences among 1–5 lie on the assembly of super tetrahedron anions by excess LnIII and TMII (TM = CoII, NiII, CuII or ZnII), which generates bigger cluster anions (complex 1–4) or anions with 1D infinite structure (complex 5). The assemble styles for synthons mentioned above show with capped style, head-to-head linking style or side-by-side linking style.

A new kind of trinuclear copper(II) motif [Cu3L] was prepared in situ by adopting a multidentate ligand, N′2,N′2′-bis(2-hydroxybenzoyl)biphenyl-2,2′-dicarbohydrazide (H6L), in the presence of a series N-containing agents. Featuring five different assembly styles, [Cu3L(DMF)2.5(hmta)]·3H2O (1), [Cu3L(DMA)(H2O)(Hmor)] (2), [Cu3L(py)2]·DMF (3), [Cu3L(DMF)(H2O)]·2DMF (4), and [Cu3L(DMA)(H2O)]·0.5DMA (5) (hmta = hexamethylenetetramine, Hmor = morphiline, py = pyridine) were obtained. In these assemblies, the [Cu3L] units are connected with each other into one-dimensional chains via bridging of N-containing agents or via sharing an oxygen atom of L6− to fuse together. Furthermore, the connecting styles are found to be governed by the character of the N-containing agents used, which is discussed in detail. Thermal gravimetric analysis and magnetic measurement of some complexes were performed.

A 3-fold interpenetrated uninodal 5-connected zfy network, based on a trigonal bipyramid Zn2(CO2)2(NN) unit, with excellent chemical and thermal stability has been synthesized, which shows triple aromatic walls and nanoscale one-dimensional square channels.

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.

Host–guest encapsulation of electron-rich naphthalene molecules into a weakly emissive porous metal–organic framework based on π-electron-deficient (π-acidic) naphthalene diimide tectons leads to orange-emissive crystals, which can be used to sense strongly basic organic amines in a fast response, high photostability, and tunable sensitivity. Moreover, such host–guest inclusion crystals are also a good photochromic probe for the detection of weakly basic N-methyl-2-pyrrolidone and N,N-dimethylformamide molecules.

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.

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.

The asymmetric unit of the title coordination polymer, [Gd(2)(C(7)H(4)O(5)S)(2)(C(2)O(4))(H(2)O)(6)](n) or [Gd(2-SB)(ox)(0.5)(H(2)O)(3)](2n) (2-SB is 2-sulfonatobenzoate and ox is oxalate), (I), consists of one Gd(III) ion, one 2-SB anion, three coordinated water molecules and one half of an ox ligand. The ox ligand is located on a crystallographic inversion centre. The Gd(III) centre shows a distorted tricapped trigonal-prismatic coordination formed by nine O atoms from two 2-SB anions, one ox ligand and three coordinated water molecules. The carboxylate and sulfonate groups of the 2-SB anions adopt μ(2)-η(1):η(2) and μ(1)-η(0):η(0):η(1) coordination modes to link two Gd(III) ions, generating a centrosymmetric binuclear [Gd(2)(2-SB)(2)(H(2)O)(6)](2-) subunit. The ox ligand acts as a bridge, linking the binuclear [Gd(2)(2-SB)(2)(H(2)O)(6)](2-) subunits into a one-dimensional chain structure parallel to the b axis. Furthermore, extensive O-H···O hydrogen bonds connect the chains into a three-dimensional supramolecular architecture.

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...

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...

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...

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.

The aqueous two-phase system formed by the mixture of dodecyltrimethylammonium bromide (DTAB) with a gemini surfactant O,O′-bis(sodium 2-lauricate)- p -benzenediol (C 11 p PHCNa) has been studied. Two two-phase regions were observed, one was a wide region in the cationic surfactant-rich side and the other in the vicinity of R = 1:1, where R is the mixing mole ratio of DTAB to C 11 p PHCNa in global solution. Multi-lamellar vesicles are formed in the concentrated upper phase of cationic surfactant-rich systems and spherical aggregates in the concentrated bottom phase at R = 1:1. The microstructure of the solution and the phase behavior of the aqueous two-phase system strongly depended on the total concentration and the composition of the system.

A 1-D hybrid copper(I) halides, [(phen)Cu3I3] n (phen = 1,10-phenanthroline)(1) with novel D6R (double six-membered rings) Cu6I6 cores, was synthesized by solvothermal reaction and characterized by single-crystal X-ray diffraction. In 1, nitrogen atoms from phen replace two I of CuI4 tetrahedron to give distorted tetrahedral geometries (CuI2N2), then CuI2N2 tetrahedron shares corners via μ3-I to generate an extended 1-D zigzag chain. Two zigzag chains combines with one 1-D (Cu4I4) n chain containing D6R cores via μ3-I-Cu (from cores) bonds to form the infinite 1-D ribbonlike polymer along the a-axis. Furthermore, the title compound is stabilized by conspicuous C–H···I hydrogen bonds, π–π and d10–d10 metallic interactions. Experimental and theoretical optical property investigation indicates that 1 possesses semiconductor property. DFT calculation was executed to probe the electronic structure of 1. To our interest, phen act as a property control species with its π* electrons appear in the forbidden band. A hybrid copper(I) halides [(phen)Cu3I3] n containing D6R cores was structurally determined, which was stabilized by conspicuous C–H···I hydrogen bonds, π–π and d10–d10 metallic interactions and possesses semiconductor property. DFT calculation indicate phen act as a property control species with its π* electrons appear in the forbidden band.

A 2-D metal–organic hybrid framework, [(Nd2DMF12IN2)(Pb8I20)]n (HIN = isonicotinic acid) was structurally determined, which was constructed from a lanthanide metal complex and 1-D lead–iodine polymersvia a HIN ligand with mixed coordination sites.

Transformation of vesicles formed in DTAB/C11-p-PhCNa aqueous surfactant two-phase (ASTP) was observed by the transmission electron microscopy (TEM). The trans-conformation of the gemini surfactant in the aggregates was considered to be the important factor for constructing the multi-lamellar structure of the vesicle wall. The cation-π interaction between the quaternary ammonium cation and the aromatic ring in the spacer was determined by the UV-Vis spectrum analysis, which, as well as the general electrostatic attraction and hydrophobic force, contributes to the stability of the multi-lamellar structure. The concentrations of the surface-active ions were measured for understanding the mechanism of vesicle transformation. The results show that isoelectric mixing of the two components benefits the growth of vesicles both in size and wall thickness.

Three novel three-dimensional metal−organic frameworks [Ln2(tdc)3(H2O)4]n, Ln = Dy(1), Ho(2), Er(3) (H2tdc = thiophene-2,5-dicarboxylic acid) have been synthesized and characterized by single crystal X-ray diffraction (XRD), powder XRD and IR spectra. X-ray crystallography reveals that the three complexes are isostructural and exhibit an unprecedented (4,5)-connected (42·64)(42·67·8) topology, in which the lanthanide ions act as unusual 5-connected nodes. The thermal stability and UV–vis absorption spectra of the title complexes have also been studied.

Two new organically templated copper halides, (nbq)4Cu4I8 (1) and [(ipq)2(Cu5I7)] n (2) have been synthesized in the presence of nbq+ and ibq+ (nbq+ = N-(n-butyl)-quinolinium, ibq+ = N-(iso-pentyl)-quinolinium) acting as structure-directing agents(SDAs). Both of the compounds present hybrid structures with SDAs and inorganic moieties being incorporated. In 1, tetrameric Cu4I8 4− anion is composed by edge-sharing CuI4 tetrahedrons and CuI3 planar triangles. But the inorganic framework of 2 presents one-dimensional arrangement which results from the tetrahedron CuI4 and pseudo trigonal pyramid CuI3 through edge-sharing fashion. Electrostatic interactions between organic counter cations and inorganic moieties could be observed and contribute to the crystal packing. Both compounds are further characterized by IR, UV–Vis, elemental analysis, fluorescence and cyclic voltammetry.

Two pseudo-polymorphic polymers, poly[ethylenediammonium [[aquacopper(II)]-micro(4)-benzene-1,2,4,5-tetracarboxylato] dihydrate], [(C(2)H(10)N(2))[Cu(C(10)H(2)O(8))(H(2)O)].2H(2)O](n), (I), and poly[ethylenediammonium [copper(II)-micro(4)-benzene-1,2,4,5-tetracarboxylato] 2.5-hydrate], [(C(2)H(10)N(2))[Cu(C(10)H(2)O(8))].2.5H(2)O](n), (II), contain two-dimensional anionic layers, ethylenediammonium (H(2)en) cations acting as counter-ions and free water molecules. Although the topological structures of the two anionic layers are homologous, the coordination environments of the Cu(II) centres are different. In (I), the Cu(II) centre, sitting on a general position, has a square-pyramidal environment. The two independent benzene-1,2,4,5-tetracarboxylate (btc) anions rest on centres of inversion. The Cu(II) cation in (II) is located on a twofold axis in a square-planar coordination. The H(2)en cation is on an inversion centre and the btc ligand is split by a mirror plane. Extensive hydrogen-bonding interactions between the complexes, H(2)en cations and water molecules lead to the formation of three-dimensional supramolecular structures.

Two new supramolecular compounds, [Ag(4,4'-bipy)](n) [Ag(HBTC)(n) (1) and [Cu(H(2)BTC)2,2-bipy)] (2) (HBTC/H(2)BTC = 1,2,4-benzenetricarboxylate, 4,4'-bipy/2,2'-bipy = 4,4'/2,2'-bipyridine), have been synthesized and characterized by elemental analyses, IR spectra, ultraviolet-visible diffuse reflection integral spectra (UV-Vis DRIS), fluorescent spectra, thermogravimetric analysis and single crystal X-ray diffraction analysis. It is noteworthy that there were two kinds of one-dimensional stairs-chain including cationic [Ag(4,4'-bipy)(n) chain and anionic [Ag(HBTC)(n) chain in 1. Furthermore, a two-dimensional double layer supramolecular framework was constructed through coordination bonds, hydrogen bonds, pi-pi stacking interactions and Ag center dot center dot center dot O weak coordinative interactions. The one-dimensional supramolecular chain of 2 was built from combining mononuclear [Cu(H(2)BTC)(2,2'-bipy)] by inter- and intramolecular hydrogen bonding interactions. Additionally, the two complexes exhibit intense blue or olivine luminescence at room temperature. (c) 2007 Elsevier B.V. All rights reserved.

Thiosemicarbazides and their metal complexes have attracted considerable interest because of their biological activities and their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Discrete copper(II) and cadmium(II) complexes have been prepared by crystallization ofN-[2-(2-hydroxybenzoyl)hydrazinecarbonothioyl]propanamide (H3L) with Cu(CH3COO)2or Cd(NO3)2in a dimethylformamide/methanol mixed-solvent system at room temperature, affording the complexes di-μ-acetato-bis{μ4-1-[(2-oxidophenyl)carbonyl]-2-(propanamidomethanethioyl)hydrazine-1,2-diido}tetracopper(II) dimethylformamide disolvate, [Cu4(C11H10N3O3S)2(C2H3O2)2]·2C3H7NO, (I), and bis{μ2-[(2-hydroxyphenyl)formamido](propanamidomethanethioyl)azanido}bis[(4,4′-bipyridine)nitratocadmium(II)] dihydrate, [Cd2(C11H12N3O3S)2(NO3)2(C10H8N2)2]·2H2O, (II). Complex (I) consists of four CuIIcations, two μ4-bridging trianionic ligands and two μ2-bridging acetate ligands, while complex (II) is composed of two CdIIcations, two μ2-bridging monoanionic ligands, two nitrate ligands and two 4,4′-bipyridine ligands. These discrete complexes are connected by hydrogen bonds and van der Waals interactions to form a three-dimensional supramolecular architecture. Compared with (I), the phenolic hydroxy group and hydrazide N atom of the thiosemicarbazide ligand of (II) are not involved in coordination and lead to a binuclear CdIIcomplex. This different coordination mode may be attributed to the larger ionic radius of the CdIIion compared with the CuIIion.

Lone pair–π interaction is an important but less studied binding force. Generally, it is too weak to influence the physical properties of supramolecular systems. Herein we reported the first example exhibiting the impact of lone pair–π interactions on photochromic properties of naphthalene diimide based coordination networks. In three isostructural 1-D networks, [(DPNDI)ZnX2] (DPNDI = N,N-di(4-pyridyl)-1,4,5,8-naphthalene diimide, X = Cl for 1, X = Br for 2 and X = I for 3), they exhibit different electron-transfer photochromic behaviors due to different lone pair–π interactions between the capped halogen atoms and electron-deficient DPNDI moieties. Specifically, 1 and 2 but not 3 are photochromic, which is attributed to a stronger lone pair–π interaction in 3 than those in 1 and 2. This study anticipates breaking a new path for designing novel photochromic materials through such unnoticeable supramolecular interactions.

We have successfully developed a new synthetic approach to modulate the electrostatic potentials of metallocavitands and thus their selective recognition towards substituted benzene derivatives via integrating two metal cations of different electronegativity into a self-assembled system.

A panchromatic hybrid crystal of anionic iodoplumbate nanowires and J-aggregated protonated naphthalene diimides has been formed through charge-assisted anion–π and lone pair–π interactions, which exhibits unusually long-lived charge-separated states even upon the irradiation of indoor lighting.

A novel organic–inorganic hybrid coordination polymer {[Cu(II)(DETA)I·DMF]2[Pb2I6]} n (DETA = diethylene triamine, DMF = N,N′-dimethyl formamide) was synthesized by the reaction of CuSO4·6H2O, DETA, Pb(NO3)2 and NaI in DMF/H2O mixed solvent at room temperature. Structural characterization of X-ray single diffraction reveals that the polymeric negative chain [Pb2I6] n 2− is built up by face-sharing of PbI6 octahedrons. Upon the hydrogen bonds interaction between N–H···I and N–H···O, structure-directing reagent chain {[Cu(II)(DETA)I·DMF]2} n 2+ presents one-dimension arrangement. Structure-directing reagent chains and polymeric negative chains are in combination with each other by static attracting force to form the so-called hybrid structure. The title compound was further characterized by IR, EA, UV-Vis and fluorescence spectrum.

Two new organically templated silver iodides, namely [(bmph)(Ag5I7)]n (1) and [(Hteda)4(Ag12I16)]n (2), have been synthesized with bmph2+ and teda [bmph2+ = 1,6-bis(4-methylpyridinio)hexane, Hteda = protonated triethylenediamine] as structure-directing agents. Complex 1 consists of a one-dimensional polymer that can be described as edge-sharing AgI4 tetrahedra, whereas 2 is the first example of a three-dimensional Ag/I framework based on Ag···Ag weak interactions and an organic template. Electrostatic interactions between the organic countercations and inorganic moieties are present and contribute to the crystal packing. Both compounds have been further characterized by IR spectroscopy, elemental analysis, TGA, and optical limiting measurements. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)