Static Retention of Dynamic Chiral Arrangements for Achiral Shear Thinning Metal-Organic Colloids.

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.

Solvent-assisted planar structure of a stilbene-based salicylhydrazone compound: crystal structure, solvent- and aggregation-induced emission, and switchable luminescence colouration.

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, CHNO·2CHOS 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 P2/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.

Four isostructural lanthanide(III) coordination compounds based on a new N-oxydic pyridyl naphthalenediimide ligand: synthesis and characterization.

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-κO,O')lanthanide]-bis{μ-N,N'-bis[(1-oxidopyridin-1-ium-3-yl)methyl]-1,8:4,5-naphthalenetetracarboxdiimide-κO:O'}-[tris(nitrato-κO,O')lanthanide]-μ-N,N'-bis[(1-oxidopyridin-1-ium-3-yl)methyl]-1,8:4,5-naphthalenetetracarboxdiimide-κO:O'] methanol disolvate], {[Ln(CHNO)(NO)]·CHOH}, with Ln = Eu, 1, Gd, 2, Dy, 3, and Er, 4, have been successfully synthesized under hydrothermal conditions.

Two novel donor-acceptor hybrid heterostructures with enhanced visible-light photocatalytic properties.

The ternary combination of metal cations, CuI and viologen based carboxylate leads to two donor-acceptor hybrid heterostructures with novel cuprous iodide clusters and narrow energy gaps. Thanks to the facilitated electron transfers between both donor and acceptor components, these unique hybrids exhibit enhanced photocatalytic degradation activities towards organic dyes under visible light irradiation in comparison with those of bulk CuI and viologen semiconductors.

A two-dimensional Cd coordination polymer based on naphthalenediimide: synthesis, crystal structure and photochromic properties.

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).

Assembly of donor-acceptor hybrid heterostructures based on iodoplumbates and viologen coordination polymers.

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.

Synthesis and characterization of a photochromic magnesium(II) coordination polymer based on a naphthalene diimide ligand.

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 (HBBNDI).

Construction of a bicontinuous donor-acceptor hybrid material at the molecular level by inserting inorganic nanowires into porous MOFs.

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.

Encapsulating Naphthalene in an Electron-Deficient MOF to Enhance Fluorescence for Organic Amines Sensing.

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.

Two-semiconductive-component hybrid coordination polymers with controllable photo-induced electron-transfer properties.

Two semiconductive inorganic-organic hybrid coordination polymers constructed from metal iodide clusters and naphthalene diimide semiconductive components, [Cu2I2(DPNDI)]n () and [PbI2(DPNDI)]n () (DPNDI = N,N'-di-(4-pyridyl)-1,4,5,8-naphthalene diimide), have been synthesized and characterized. Although possessing similar 2D heterostructures, hybrids exhibited different photo-induced electron-transfer properties. Due to the higher HOMO energy level of the [Cu2I2]n chain than that of the [PbI2]n cluster, only hybrid can easily undergo intramolecular electron transfer to form a long-lived charge separated state, which may be applied in artificial photosynthesis.

Syntheses and structures of discrete copper(II) and cadmium(II) supramolecular complexes based on 1,4-diacylthiosemicarbazone ligands.

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 of N-[2-(2-hydroxybenzoyl)hydrazinecarbonothioyl]propanamide (H3L) with Cu(CH3COO)2 or Cd(NO3)2 in 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 Cu(II) cations, two μ4-bridging trianionic ligands and two μ2-bridging acetate ligands, while complex (II) is composed of two Cd(II) cations, two μ2-bridging monoanionic ligands, two nitrate ligands and two 4,4'-bipyridine ligands.

The impact of lone pair-π interactions on photochromic properties in 1-D naphthalene diimide coordination networks.

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.

Mixed-metal metallocavitands: a new approach to tune their electrostatic potentials for controllable selectivity towards substituted benzene derivatives.

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 three-dimensional cadmium(II) coordination polymer with unequal homochiral double-stranded concentric helical chains.

A homochiral helical three-dimensional coordination polymer, poly[[(μ2-acetato-κ(3)O,O':O)(hydroxido-κO)(μ4-5-nicotinamido-1H-1,2,3,4-tetrazol-1-ido-κ(5)N(1),O:N(2):N(4):N(5))(μ3-5-nicotinamido-1H-1,2,3,4-tetrazol-1-ido-κ(4)N(1),O:N(2):N(4):N(5))dicadmium(II)] 0.75-hydrate], {[Cd2(C7H5N6O)2(CH3COO)(OH)]·0.75H2O}n, was synthesized by the reaction of cadmium acetate, N-(1H-tetrazol-5-yl)isonicotinamide (H-NTIA), ethanol and H2O under hydrothermal conditions.

A panchromatic hybrid crystal of iodoplumbate nanowires and J-aggregated naphthalene diimides with long-lived charge-separated states.

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.

Photogeneration of two reduction-active charge-separated states in a hybrid crystal of polyoxometalates and naphthalene diimides.

The combination of naphthalene diimide tectons with zinc cations in the presence of polyanions, Mo6O19(2-), leads to a hybrid crystal composed of two-dimensional porous coordination networks and polyoxometalates, which can generate two kinds of long-lived charge-separated states for the reduction reactions upon irradiation.

Lone pair-π interaction-induced generation of non-interpenetrated and photochromic cuboid 3-D naphthalene diimide coordination networks.

Interpenetration is an intrinsic behaviour for the porous coordination networks. To prevent the interpenetration, a common strategy is the imposition of geometric or steric restrictions by incorporating bulky moieties into organic tectons. So far, most of the available incorporations have been achieved through a covalent connection, while few involved in the non-covalent weak interactions.

A photochromic naphthalene diimide coordination network sensitized by polyoxometalates.

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.

A pillared framework coordination polymer based on the Cd3(μ3-OH) unit: poly[[(μ4-5-aminotetrazolato-κ(4)N(1):N(2):N(3):N(4))chlorido-μ3-hydroxido-(μ3-isonicotinato-κ(3)N:O:O')dicadmium(II)] 0.14-hydrate].

The title coordination polymer, {[Cd2(CH2N5)(C6H4NO2)Cl(OH)]·0.14H2O}n, (I), was synthesized by the reaction of cadmium acetate and N-(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).

Enantioselective synthesis of a chiral coordination polymer with circularly polarized visible laser.

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.

A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[μ3-benzotriazolato-κ(3)N(1):N(2):N(3)-copper(I)].

The title complex, [Cu(C6H4N3)]n, was synthesized by the reaction of cupric nitrate, 1H-benzotriazole (BTAH) and aqueous ammonia under hydrothermal conditions. The asymmetric unit contains three crystallographically independent Cu(I) cations and two 1H-benzotriazolate ligands. Two of the Cu(I) cations, one with a linear two-coordinated geometry and one with a four-coordinated tetrahedral geometry, are located on sites with crystallographically imposed twofold symmetry.

An electron-deficient metallocavitand with an unusual selectivity towards substituted benzene derivatives during co-crystallizations.

A double-wall-hourglass-shaped metallocavitand bearing an electron-deficient cavity was self-assembled, which exhibited an unusual selectivity to substituted benzene derivatives of different electron density during co-crystallizations.

Di-μ2-chlorido-dichloridobis(dimethylformamide)tetrakis[μ3-1-(2-oxidobenzoyl)-2-(2-oxo-2-phenylethanethioyl)hydrazine-1,2-diido]octacopper(II) dimethylformamide disolvate.

The title compound, [Cu8(C15H10N3O3S)4Cl4(C3H7NO)2]·2C3H7NO, consisting of eight Cu(II) cations, four trianionic 1-(2-oxidobenzoyl)-2-(2-oxo-2-phenylethanethioyl)hydrazine-1,2-diide ligands, four chloride ligands and two coordinated and two solvent dimethylformamide molecules, crystallizes with the octanuclear molecule located on an inversion centre. The two halves of the molecule are connected by two bridging Cl atoms. This is the first example of an octanuclear complex based on a thiosemicarbazone-derived ligand.

An unusual double T5(2) water tape trapped in silver(I) coordination polymer hosts: influence of the solvent on the assembly of Ag(I)-4,4'-bipyridine chains with trans-cyclohexanedicarboxylate and their luminescent properties.

In this paper, four silver(I) compounds, namely, {[Ag(4)(bipy)(4)(chda)]·2NO(3)·10H(2)O}(n) (1), {[Ag(2)(bipy)(2)(chda)]·14H(2)O}(n) (2), {[Ag(2)(bipy)(2)(chda)]·3EG·2H(2)O}(n) (3) and {[Ag(2)(bipy)(2)(chda)]·H(2)chda}(n) (4) (where bipy = 4,4'-bipyridine, H(2)chda = trans-cyclohexane-dicarboxylate and EG = ethylene glycol), have been synthesized and characterized by single-crystal X-ray diffraction analyses. In all of these compounds, the Ag(I) centers are linked by bipy ligands to form 1D Ag(I)-bipy chain structures. The chda(2-) anions of compound 1 adopt a μ(4)-coordination mode to connect the Ag(I)-bipy chains, forming a H-beam-like chain.

trans-Diaqua-bis-[5-(pyridine-3-carboxamido)-tetra-zolido-κ(2)O,N(1)]zinc dihydrate.

The title compound, [Zn(C(7)H(5)N(6)O)(2)(H(2)O)(2)]·2H(2)O, consists of one Zn(II) ion located on the crystallographic inversion centre, two 5-(pyridine-3-carboxamido)-tetra-zolide ligands, two coordinated water mol-ecules and two free water mol-ecules. The Zn(II) ion adopts a slightly distorted octa-hedral coordination geometry formed by the N,O-chelating ligands and two O water atoms. The pyridine N atoms are not coordinated.