A Coordination-Derived Cerium-Based Amorphous-Crystalline Heterostructure with High Electrocatalytic Oxygen Evolution Activity.

The rational design of heterogeneous catalysts is crucial for achieving optimal physicochemical properties and high electrochemical activity. However, the development of new amorphous-crystalline heterostructures is significantly more challenging than that of the existing crystalline-crystalline heterostructures. To overcome these issues, a coordination-assisted strategy that can help fabricate an amorphous NiO/crystalline NiCeO (a-NiO/c-NiCeO) heterostructure is reported herein.

Construction of Highly Luminescent Lanthanide Coordination Polymers and Their Visualization for Luminescence Sensing.

NaHSIP was selected as an organic ligand (NaHSIP = 5-sulfoisophthalic acid monosodium salt). We successfully constructed a new class of lanthanide coordination polymers Ln-HS ([Ln(SIP)(DMF)(HO)]DMF·HO; Ln = Eu, Tb, Sm, and Dy) by a simple solvothermal synthesis method. They exhibited excellent photoluminescence properties for Ln ions, where Eu-HS and Tb-HS exhibited high quantum yields of 13.

Facile synthesis of an ultrathin ZIF-67 layer on the surface of Sn/Ti co-doped hematite for efficient photoelectrochemical water oxidation.

Hematite is a promising photoanode for photoelectrochemical (PEC) water splitting but its practical performance has been severely hindered by its poor conductivity and sluggish water oxidation kinetics. Metal-organic frameworks (MOFs), considered as efficient oxygen evolution catalysts (OECs), have been widely applied for PEC water splitting in recent years. Here, we modified an ultrathin (about 2 nm) Co-based ZIF-67 layer on the surface of Sn/Ti co-doped α-FeO by a simple one-step solvothermal method.

Two-dimensional heterostructures built from ultrathin CeO nanosheet surface-coordinated and confined metal-organic frameworks with enhanced stability and catalytic performance.

Two-dimensional (2D) metal-organic framework (MOF) based heterostructures will be greatly advantageous to enhance catalytic performance because they increase the contact surface and charge transfer. Herein, a novel 2D heterostructure named CeO@NiFe-MOFs, in which monolayer NiFe-MOFs is coordinated with ceria (CeO) to improve catalytic and stability performance, is successfully constructed by the strategy of growth on the surface of ultrathin CeO nanosheets being functionalized with monolayer carboxylic acid groups. The 2D heterostructure possesses a sandwich structure, where monolayer NiFe-MOFs are coordinated to both the top and bottom surface of CeO nanosheets joining carboxylic acid groups.

Synthesis and optical and electronic properties of one-dimensional sulfoxonium-based hybrid metal halide (CH)SOPbI.

We report the synthesis and optical and electronic properties of a one-dimensional sulfoxonium-based hybrid metal halide in an orthorhombic crystal system with a Pnma space group. To provide direct insights, a method is developed to calculate tolerance factors with the ionic radii of non-spherical cations from X-ray crystallographic data.

A new 3-D coordination polymer as a precursor for CuI-based thermoelectric composites.

Two complexes, [Cu6I6(L1)3]n (I) and [Cu4I4(L2)2]n (II) (L1 = 1,4-bis(phenylthio)but-2-yne; L2 = 1,4-bis(phenylthio)butane), as precursors for thermoelectric composites were prepared using a literature procedure. During the preparation of I, an unexpected 3-D polymorph [Cu4I4(L1)2]n (1) with a triclinic space group and an infinite [CuI]n staircase structure was obtained. This new polymorph (1) exhibited the same structure at both room temperature and 173 K.

A thermoelectric copper-iodide composite from the pyrolysis of a well-defined coordination polymer.

Coordination polymer 1 was prepared from CuI and a flexible [SNS] ligand L in acetonitrile. The thermal decomposition of 1 yielded a CuI-rich thermoelectric carbon composite 2, which is relatively light, thermally stable and robust. Composite 2 possesses high Seebeck coefficients (700-950 μV K-1) from rt to 204 °C after an optimization cycle.

Hydrogen-Bonding Interactions in Luminescent Quinoline-Triazoles with Dominant 1D Crystals.

Quinoline-triazoles 2-((4-(diethoxymethyl)-1-1,2,3-triazol-1-yl)methyl)quinoline (), 2-((4-(m-tolyl)-1-1,2,3-triazol-1-yl)methyl)quinoline () and 2-((4-(p-tolyl)-1-1,2,3-triazol-1-yl)methyl)quinoline () have been prepared with CuAAC click reactions and used as a model series to probe the relationship between lattice H-bonding interaction and crystal direction of growth. Crystals of - are 1D tape and prism shapes that correlate with their intermolecular and solvent 1D lattice H-bonding interactions. All compounds were thermally stable up to about 200 C and blue-green emissive in solution.

Electrostatic-Driven Exfoliation and Hybridization of 2D Nanomaterials.

Here, direct and effective electrostatic-driven exfoliation of tungsten trioxide (WO ) powder into atomically thin WO nanosheets is demonstrated for the first time. Experimental evidence together with theoretical simulations clearly reveal that the strong binding of bovine serum albumin (BSA) on the surface of WO via the protonation of NH groups in acidic conditions leads to the effective exfoliation of WO nanosheets under sonication. The exfoliated WO nanosheets have a greatly improved dispersity and stability due to surface-protective function of BSA, and exhibit a better performance and unique advantages in applications such as visible-light-driven photocatalysis, high-capacity adsorption, and fast electrochromics.

Multicomponent (Ce, Cu, Ni) oxides with cage and core-shell structures: tunable fabrication and enhanced CO oxidation activity.

Solvothermal synthesis of Cu2O cubes from Cu(OAc)2 in ethanol provided templates for tunable formation of novel multicomponent composites: hollow CeO2-Cu2O (), core-shell NiO@Cu2O () and hollow CeO2-NiO-Cu2O (). Composites catalyze the oxidation of CO at a lower temperature than the parent Cu2O cubes.

High-Level Incorporation of Silver in Gold Nanoclusters: Fluorescence Redshift upon Interaction with Hydrogen Peroxide and Fluorescence Enhancement with Herbicide.

High-level incorporation of Ag in Au nanoclusters (NCs) is conveniently achieved by controlling the concentration of Ag(+) in the synthesis of bovine serum albumin (BSA)-protected Au NCs, and the resulting structure is determined to be bimetallic Ag28 Au10-BSA NCs through a series of characterizations including energy-dispersive X-ray spectroscopy, mass spectroscopy, and X-ray photoelectron spectroscopy, together with density functional theory simulations. Interestingly, the Ag28 Au10 NCs exhibit a significant fluorescence redshift rather than quenching upon interaction with hydrogen peroxide, providing a new approach to the detection of hydrogen peroxide through direct comparison of their fluorescence peaks. Furthermore, the Ag28 Au10 NCs are also used for the sensitive and selective detection of herbicide through fluorescence enhancement.

A Triazolyl-Pyridine-Supported Cu Dimer: Tunable Luminescence and Fabrication of Composite Fibers.

The dinuclear complex [Cu I (L1) ] (1) (L1=3-((4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)methyl)benzonitrile) is characterized by single-crystal X-ray diffraction (XRD), powder XRD, IR, photoluminescence spectroscopy, and thermogravimetric analysis. Unlike other related, known copper iodide complexes, it exhibits strong yellow emission in the solid state at both room temperature and 77 K. Showing good compatibility with PMMA, it is blended with the polymer in different weight ratios to prepare luminescent composite fibers.

Luminescent [Cu₄I₄] aggregates and [Cu₃I₃]-cyclic coordination polymers supported by quinolyl-triazoles.

Quinolyl-1,2,3-triazole ligand supported [Cu4I4] stair-step aggregates [Cu4I4(L1)2] (1), [Cu4I4(L2)2] (2), [Cu4I4(L3)2] (3), [Cu4I4(L4)2] (4), [Cu4I4(L5)2] (5), and six-membered [Cu3I3] metallacycle based coordination polymers [Cu2I2(L6)]n (6) and [Cu2I2(L7)]n (7) (ligands are 2-((1H-1,2,3-triazol-1-yl)methyl)quinoline (L1), 2-((4-alkyl-1H-1,2,3-triazol-1-yl)methyl)quinoline (propyl, butyl and isobutyl for L2, L3 and L4, respectively) and 2-(1-((quinolin-2-yl)methyl)-1H-1,2,3-triazol-4-yl)alcohol (methanol, ethanol and propanol for L5, L6 and L7, respectively)) have been prepared and characterized by single-crystal X-ray diffraction (XRD), powder XRD, photoluminescence spectroscopy and thermogravimetric analysis. Complexes 1-5 are stair-step [Cu4I4] aggregate structures supported by two quinolyl-triazole hybrid ligands. Complexes 6 and 7 are rare cyclic [Cu3I3] aggregate-based 1-D coordination polymers.

A fluorescent light-up platform with "AIE + ESIPT" characteristics for multi-target detection both in solution and on paper strip.

We report a fluorescent light-up platform for multi-target detection in aqueous solution and on paper strip. The platform is based on a salicylaldazine fluorogen with aggregation-induced emission (AIE) and excited state intramolecular proton transfer (ESIPT) characteristics, which shows distinct advantages including ease of chemical modifications, free of self-quenching effect, excellent light-up ratio and large Stokes shift. To demonstrate the versatility of the platform, palladium cation and perborate anion, as well as UV light, were selected as the targets.

Dianthraceno[a,e]pentalenes: synthesis, crystallographic structures and applications in organic field-effect transistors.

Two soluble and stable dianthraceno[a,e]pentalenes with two (DAP1) and six (DAP2) phenyl substituents were synthesized. Both compounds possess a small energy band gap and show amphoteric redox behaviour due to intramolecular donor-accepter interactions. X-ray crystallographic analysis revealed that DAP2 has a closely packed structure with multi-dimensional [C-H···π] interactions although there are no π-π interactions between the dianthraceno[a,e]pentalene cores.

Recent advances in C-S bond formation via C-H bond functionalization and decarboxylation.

The development of mild and general methods for C-S bond formation has received significant attention because the C-S bond is indispensable in many important biological and pharmaceutical compounds. Early examples for the synthesis of C-S bonds are generally limited to the condensation reaction between a metal thiolate and an organic halide. Recent chemical approaches for C-S bond formation, based upon direct C-H bond functionalization and decarboxylative reactions, not only provide new insights into the mechanistic understanding of C-S coupling reactions but also allow the synthesis of sulfur-containing compounds from more effective synthetic routes with high atom economy.

Destabilization of gold clusters for controlled nanosynthesis: from clusters to polyhedra.

A precisely controlled destabilization of gold thiolate clusters is demonstrated to grow 12 {110}-faceted gold dodecahedra with greatly enhanced catalytic capability, and reveal the growth mechanism by DFT simulations. This greatly advances our understanding of nanocrystal growth and opens a new window for controlling the dissociation of clusters to produce nanocrystals with specific shapes.

Carboxylate-rich hybrid ligands in Mn(II) complexes as precursors for water oxidation reactions.

A new family of Mn(II) complexes stabilized by carboxylate-rich hybrid ligands has been synthesized, characterized and applied as catalytic precursors for MnO2 nanoparticles in water oxidation by (NH4)2Ce(NO3)6.

Hybrid NS ligands supported Cu(I)/(II) complexes for azide-alkyne cycloaddition reactions.

Three copper complexes of nitrogen-sulfur donor ligands, [CuBr₂(L1)] (1), [CuCl₂(L2)₂] (2) and [Cu₂I₂(L3)]n (3) (L1 = bis(2-cyclohexylsulfanylethyl)amine, L2 = 2-(benzylsulfanylmethyl)pyridine and L3 = 2-(4-pyridylsulfanylmethyl)pyridine), have been synthesized and characterized by single-crystal X-ray diffraction (XRD), powder XRD and TGA analysis. Complexes 1 and 2 are mononuclear Cu(II) complexes and are EPR active with distorted square-pyramidal and octahedral geometry, respectively. Complex 3 is a two-dimensional tetrahedral Cu(I) coordination polymer with 16- and 20-membered metallocycles.

"Click-and-click"--hybridised 1,2,3-triazoles supported Cu(I) coordination polymers for azide-alkyne cycloaddition.

Two novel pyridyl and thioether hybridised 1,2,3-triazole ligands 1-(2-picolyl)-4-(2-(methylthio)-pyridine)-1H-1,2,3-triazole (L1) and 1-(4-picolyl)-4-(2-(methylthio)-pyridine)-1H-1,2,3-triazole (L2) were prepared from CuAAC click reactions. Reactions of CuI with the ligands L1 and L2 yielded two one-dimensional coordination polymers [Cu6I6(L1)2]n (1) and [Cu2I2(L2)2]n (2). Single-crystal X-ray diffraction reveals that 1 and 2 are polymeric with [Cu6I6] and [Cu2I2] respectively as building blocks.

Trans [O=Re(V)-OH] core stabilised by chelating N-heterocyclic dicarbene ligands.

Three Re(v) N-heterocyclic carbene complexes [ReO(OH)(L(Me))(2)][PF(6)](1.4)[ReO(4)](0.6), [ReO(OH)(L(iPr))(2)][PF(6)](1.

Chelating Schiff base assisted azide-bridged Mn(II), Ni(II) and Cu(II) magnetic coordination polymers.

Four new Mn(II), Ni(II) and Cu(II) coordination polymers [Mn2(L1)(μ(1,1)-N3)2(μ(1,3)-N3)2]n (1), [Ni(L2)2(μ(1,3)-N3)]n(ClO4)n (2), [Cu(L3)(μ(1,1)-N3)(N3)]n (3) and [Cu(L4)(μ(1,1)-N3)2]n (4) (L1 = N,N′-bis(2-pyridylmethylene)ethane-1,2-diamine, L2 = N-(2-pyridylmethylene)methylamine, L3 = N-(2-pyridylmethylene)-3-pyridylamine, L4 = N-(2-pyridylmethylene)-tbutylamine) have been synthesized and characterized by single-crystal X-ray analysis and magnetic measurements. Complex 1 indicates a stoichiometry-dependent structural change (based on Mn:L1:N3 = 2:1:4 molar ratio) and consists of two-dimensional (2-D) (4,4) net layers, in which Mn(II) centers are co-bridged by single end-to-end (EE), double end-on (EO) azide and chelate-bridging L1 ligands. Complex 2 shows a single EE azide-bridged one-dimensional (1-D) Ni(II) chain.

N-heterocyclic carbene Pt(II) complexes from caffeine: synthesis, structures and photoluminescent properties.

The caffeine-derived N-heterocyclic carbene (NHC) complex [Pt(II)(C^N)(NHC)Cl] (C^N = 2-phenylpyridine), 4 has the opposite stereochemistry and a shorter Pt-C(carbene) bond compared to that of an analogous benzimidazole-derived N,N-heterocyclic carbene (NNHC) Pt complex 2. These suggest a lower trans influence of pyridyl N compared to cyclometallated carbon and an increased Pt-NHC π-backbonding because of decreased π-donation resulting from conjugation to the electron deficient pyrimidine of caffeine. Complex 4 has a lower emission quantum yield (Φ) and is blue-shifted into the green region of the visible spectrum relative to non-carbene Pt(II) cyclometalated complex 5.

Nitrogen-rich azoles as ligand spacers in coordination polymers.

N-heterocycle-based ligands are versatile building-blocks for coordination oligomer and polymer assemblies of first-row transition metals. Herein, we review recent developments in the design and synthesis of some nitrogen-rich azole-based ligands, their assembly modes in coordination oligomers and polymers, and the potential applications of the resulting metallosupramolecules.

Functionalized 1,2,3-triazoles as building blocks for photoluminescent POLOs (polymers of oligomers) of copper(I).

Two 3-D and one 2-D metal-organic frameworks [Cu(8)I(8)(L1)(4)](n) (1), [Cu(8)I(8)(L2)(4)](n) (2) and [Cu(4)I(4)(L3)(2)](n) ()3 were synthesized using three novel pyridine and pyrazole supported 1,2,3-triazoles, 1-(4-picolyl)-4-butyl-1H-1,2,3-triazole (L1), 1-(4-picolyl)-4-pentyl-1H-1,2,3-triazole (L2) and 1-(4-picolyl)-4-(3,5-dimethylpyrazolylmethyl)-1H-1,2,3-triazole (L3). In both complexes 1 and 2, there co-exist a 1-D Cu(I) oligomer and Cu(4) tetrahedron cluster in the 3-D polymeric structures. Complex 3 shows a 2-D (4, 4) net with the stair-step Cu(4)I(4) as node and L3 as a building block.