Enantiopure trigonal bipyramidal coordination cages templated by in situ self-organized D-symmetric anions.

The control of a molecule's geometry, chirality, and physical properties has long been a challenging pursuit. Our study introduces a dependable method for assembling D-symmetric trigonal bipyramidal coordination cages. Specifically, D-symmetric anions, like oxalate and chloranilic anions, self-organize around a metal ion to form chiral-at-metal anionic complexes, which template the formation of D-symmetric trigonal bipyramidal coordination cages.

Two-Dimensional Spin-Crossover Molecular Solid Solutions with Tunable Transition Temperatures across 90 K.

Spin-crossover (SCO) materials exhibit remarkable potential as bistable switches in molecular devices. However, the spin transition temperatures () of known compounds are unable to cover the entire ambient temperature spectrum, largely limiting their practical utility. This study reports an exemplary two-dimensional SCO solid solution system, = 5--2-hydroxybenzylidene-hydrazinecarbothioamide, = F or Cl, = 0 to 1), in which the adjacent layers are adhered via hydrogen bonding.

Engineering the Sulfide Semiconductor/Photoinactive-MOF Heterostructure with a Hollow Cuboctahedral Structure to Enhance Photocatalytic CO-Epoxide-Cycloaddition Efficiency.

Providing efficient electronic transport channels has always been a promising strategy to mitigate the recombination of photogenerated charge carriers. In this study, a heterostructure composed of a semiconductor/photoinactive-metal-organic framework (MOF) was constructed to provide innovative channels for electronic transport. Prepared using a previously reported method ( 2016, 55, 15301-15305) with slight modifications to temperature and reaction time, the CuS@HKUST-1 hollow cuboctahedron was synthesized.

Engineering cuboctahedral N-doped C-coated p-CuO/n-TiO heterojunctions toward high-performance photocatalytic cross-dehydrogenative coupling.

The low separation efficiency of photogenerated electron-hole (e-h) pairs severely limits the activation of photocatalyts. One brilliant strategy is to construct a p-n type semiconductor heterojunction, which can establish an inner electric field to separate the e-h pairs with high efficiency. Here, for the first time, a cuboctahedral N-doped carbon-coated CuO/TiO p-n heterojunction (CuO-TiO@N-C) was designed and fabricated successfully direct calcination of a benzimidazole-modulated cuboctahedral HKUST-Cu with titanium-tetraisopropanolate absorbed inside concomitantly.

Successive syntheses and magnetic properties of homodinuclear lanthanide macrocyclic complexes.

A series of homodinuclear β-diketone lanthanide(III) complexes, formulated as [(acac)Ln(L1)] (Ln = Dy (1), Tb (2), and Gd (3), respectively) were first synthesized based on a closed-macrocyclic ligand (HL1) derived from the [2 + 2] cyclocondensation of 4--butyl-2,6-diformylphenol and -phenylenediamine in the presence of lanthanide acetylacetonates. Subsequently, by using the above compounds as building blocks to assemble directly with another Schiff base ligand, ,'-bis(5-chlorosalicylidene)--phenylenediamine (HL2), three new homodinuclear sandwich-type lanthanide complexes with the general formula [Ln(L1)(L2)] (Ln = Dy (4), Tb (5), and Gd (6), respectively) were further designed and prepared. Single-crystal X-ray analyses show that the central Ln ion adopts a distorted square antiprism conformation with local symmetry.

Magnetic Relaxation Studies on Trigonal Bipyramidal Cobalt(II) Complexes.

We report the preparation and the full characterization of a novel mononuclear trigonal bipyramidal Co complex [Co(NS )Br](BPh ) (1) with the tetradentate sulfur-containing ligand NS (N(CH CH SCH(CH ) ) ). The comparison of its magnetic behaviour with those of two previously reported compounds [Co(NS )Cl](BPh ) (2) and [Co(NS )Br](ClO ) (3) (NS =N(CH CH SC(CH ) ) ) with similar structures shows that 1 displays a single-molecule magnet behaviour with the longest magnetic relaxation time (0.051 s) at T=1.

Hierarchical multi-shell 66-nuclei silver nanoclusters trapping subvalent Ag kernels.

Hierarchical nano structures are hard to fabircate. Here, we present three novel hierarchical multi-shell 66-nuclei silver nanoclusters, trapping ultrasmall Ag64+ nano-fragments by nine MoO42- ions. This Ag6@(MoO4)9 core is further wrapped by an outer Ag60 shell.

An All-Alkynyl Protected 74-Nuclei Silver(I)-Copper(I)-Oxo Nanocluster: Oxo-Induced Hierarchical Bimetal Aggregation and Anisotropic Surface Ligand Orientation.

The hardness of oxo ions (O ) means that coinage-metal (Cu, Ag, Au) clusters supported by oxo ions (O ) are rare. Herein, a novel μ -oxo supported all-alkynyl-protected silver(I)-copper(I) nanocluster [Ag Cu O (PhC≡C) ] (NC-1, avg. x=37.

Spin switching in tris(8-aminoquinoline)iron(ii)(BPh): quantitative guest-losing dependent spin crossover properties and single-crystal-to-single-crystal transformation.

As a derivative of 2-picolylamine, which contains rich protons favouring hydrogen bond formation to assemble a variety of valuable spin crossover (SCO) compounds, 8-aminoquinoline (aqin) will be a good candidate for constructing new mononuclear bistable state compounds. With the guidance of this view, two solvated compounds [Fe(aqin)3](BPh4)2·2(CH3CN) (1·2CH3CN) and [Fe(aqin)3](BPh4)2·1.5(CH3COCH3) (2·1.

Half-sandwich lanthanide crown ether complexes with the slow relaxation of magnetization and photoluminescence behaviors.

Four half-sandwich type mononuclear lanthanide crown ether complexes with the formula [Ln(12-crown-4)(NO)] (Ln = Dy (1), Tb (2), Ho (3), and Er (4); 12-crown-4 = 1,4,7,10-tetraoxacyclododecane) were successfully synthesized and structurally characterized. Ac magnetic susceptibility measurements reveal that dysprosium complex 1 behaves as a typical single-ion magnet, while solid state photoluminescence studies show that complexes 1 and 2 have the respective lanthanide(iii) luminescence characteristics.

Syntheses, structures, and magnetic properties of homodinuclear lanthanide complexes based on dinucleating Schiff base ligands.

The first two families of homodinuclear lanthanide(III) complexes, formulated as [(L(OEt))2Ln2(L1)] and [(LOEt)2Ln2(L2)] (Ln(3+) = Dy(3+), Tb(3+), Ho(3+), Gd(3+), and Y(3+); L1(4-) = 2,2',2'',2'''-[1,2,4,5-benzenetetrayltetrakis(nitrilomethylidyne)]tetrakisphenolate; L2(4-) = 2,2',2'',2'''-[[1,1'-biphenyl]-3,3',4,4'-tetrayltetrakis(nitrilomethylidyne)]tetrakis(4-chlorophenolate); L(OEt)(-) = (η(5)-cyclopentadienyl)tris(diethylphosphito-p)cobaltate(III)), were successfully synthesized based on Kläui's tripodal building block NaL(OEt) and two dinucleating Schiff base ligands, H(4)L1 and H(4)L2, respectively. Single-crystal X-ray analyses show that these lanthanide complexes have two seven-coordinated metal binding sites, linked to each other with a phenyl or biphenyl bridge. Variable temperature dc magnetic measurements reveal the weakly antiferromagnetic coupling between paramagnetic lanthanide ions, while ac magnetic data exhibit the field-induced relaxation of magnetization for the corresponding Dy2 complexes 1 and 6.

Measuring motion trajectories of particle swarms in flight.

We propose a novel dual optimization framework for measuring motion trajectories of large swarms of natural particles, in which a continuous objective model is defined in form of energy to approximate faithfully the behaviors of moving targets. Following the Lagrange dual decomposition strategy, the framework distributes the optimization problem into simple subproblems, each of which also approximate different behavior of targets respectively. With this "realistic" energy, the proposed scheme can approximate the underlying posterior of problems faithfully, while avoiding discretization errors.

Aggregation-induced emissive copper(I) complexes for living cell imaging.

Phosphorescent binuclear copper(I) complexes [Cu2(BrphenBr)2(Ph2P(CH2)nPPh2)2](ClO4)2 with different conformations are obtained by reaction of [Cu(NCCH3)4]ClO4, 3,8-dibromo-1,10-phenanthroline (BrphenBr), and corresponding diphosphine ligands, where n = 1, 4, 5, and 6 in complexes Cu-1, Cu-2, Cu-3, and Cu-4, respectively. Complex Cu-4 exhibits both the eclipsed and the staggered conformations of 18-membered Cu2C12P4 metallacycles in a 1:1 ratio in the crystal structure. All complexes are very stable to air and moisture in the solid state because of the high level of protection of all the Cu(I) centers, N and P atom centers resulting from the close contact of BrphenBr and diphosphine ligands, and what is more important is that there exist very soft P donors and the chelating effect of aromatic N atoms.

Temperature-dependent in situ ligand cyclization via C═C coupling and formation of a spin-crossover iron(II) coordination polymer.

The reaction of N(1),N(2)-bis(pyridin-4-ylmethylene)ethane-1,2-diamine (L) with Fe(NCS)(2) under various temperatures gave rise to three iron(II) coordination polymers, namely, one-dimensional [Fe(L')(NCS)(2)] (1), two-dimensional [Fe(L)(2)(NCS)(2)]·H(2)O (2), and one-dimensional [Fe(L)(2)(NCS)(2)]·2CH(2)Cl(2)·4MeOH (3). The formation of 1 involved an in situ C═C coupling reaction, L to L' [L' = 5,6-di(pyridin-4-yl)-1,2,3,4-tetrahydropyrazine], which was catalyzed by cyanide ions decomposed from thiocyanates; the manganese(II) (1a) and zinc(II) (1b) analogues of 1 were also synthesized for comparison. Magnetic studies showed that complex 1 underwent a pressure-dependent one-step incomplete spin transition whereas complexes 2 and 3 were paramagnetic in the whole temperature range.

An iron(II) incomplete spin-crossover compound: pressure effects and Mössbauer spectroscopy study.

A one-dimensional iron(II) spin-crossover compound [Fe(3py-im)(2)(NCS)(2)].7H(2)O (1) (3py-im = 2,4,5-tris(4-pyridly)-imidazole) has been solvothermally synthesized and structurally characterized. Compound 1 crystallizes in the monoclinic space group P2/c with a = 11.

The effects of pressure on valence tautomeric transitions of dinuclear cobalt complexes.

The effects of pressure on valence trautomeric transition behavior of two complexes, [{Co(tpa)}2(dhbq)].(PF6)3 (.(PF6)3) and [{Co(dpqa)}2(dhbq)](PF6)3 (II x (PF6)3) (tpa = tris(2-pyridylmethyl)amine, dpqa = di(2-pyridylmethyl)-N-(quinolin-2-ylmethyl)amine and dhbq = deprotonated 2,5-dihydroxy-1,4-benzoquinone), in the light of changes of magnetic susceptibilities were investigated; the results show that external pressure makes the SC + ET transition process of the two complexes into a general SC process only.