Selective oxidation of β-keto ester modulated by the d-band centers in D-A conjugated microporous metallaphotoredox catalysts containing M-salen (MZn, Cu and Co) and triazine monomers.

Photocatalytic selective oxidation plays an important role in developing green chemistry. However, it is challenging to design an efficient photocatalyst for controlling the selectivity of photocatalytic oxidation reaction and exploring its detailed mechanism. Here, we synthesized three conjugated microporous polymers (CMPs) with D-A structures, named M-SATE-CMPs (MZn, Cu and Co), with different d-band centers based on different metal centers, resulting in the discrepancy in adsorption and activation capacities for the reactants, which produces the selectivity of β-keto esters being catalyzed into α-hydroperoxide β-keto esters (ROOH) or to α-hydroxyl β-keto esters (ROH).

A linker conformation induced metal-organic framework with high stability and efficient upgrading of natural gas.

Natural gas plays an important role in daily life and the petrochemical industry, but there are often large amounts of impurities which prevent the full use of methane in natural gas. Developing excellent adsorbents to purify CH from multi-component mixtures is crucial, but also faces great challenges. Here, by utilizing a ligand conformation preorganization strategy, we employ a flexible nonplanar hexacarboxylate ligand with 2 symmetry to successfully construct a robust microporous metal-organic framework {[Cu(bmipia)(HO)]·(DMF)(CHCN)} (GNU-1, bmipia = 5-[,-bis(5-methylisophthalic acid)amion] isophthalate) with an unprecedented topology.

Fabrication of a lead-free ternary ceramic system for high energy storage applications in dielectric capacitors.

The importance of electroceramics is well-recognized in applications of high energy storage density of dielectric ceramic capacitors. Despite the excellent properties, lead-free alternatives are highly desirous owing to their environmental friendliness for energy storage applications. Herein, we provide a facile synthesis of lead-free ferroelectric ceramic perovskite material demonstrating enhanced energy storage density.

A Nanocluster [AgCl(SPhBu)]: Chloride Intercalation, Specific Electronic State, and Superstability.

The controlling synthesis of novel nanoclusters of noble metals (Au, Ag) and the determination of their atomically precise structures provide opportunities for investigating their specific properties and applications. Here we report a novel silver nanocluster [AgCl(SPhBu)] (Ag) whose structure is determined by X-ray single crystal diffraction. The structure analysis shows that nanocluster Ag contains a Ag core, a surface shell of [AgClS], and a Cl intermediate layer located between Ag and [AgClS].

Synthesis, structural characterization and antitumor activity of six rare earth metal complexes with 8-hydroxyquinoline derivatives.

The rare earth metal Gd(III), Yb(III), Lu(III), Eu(III), Tb(III) and Ho(III) complexes 1-6 with 2-((2-(pyridin-2-yl)hydrazono)methyl)quinolin-8-ol (H-L) as ligands were synthesized. The in vitro cytotoxicity assay indicated that the cytotoxicity of 1 was equivalent to cisplatin and higher than that of H-L and other complexes towards T24 tumor cells. The mechanism study indicated that 1 caused significant up-regulation of the proteins p27, p21 and p53 in T24 cells and cell cycle arrest in G2 phase.

A Discrete Tetrahedral Indium Cage as an Efficient Heterogeneous Catalyst for the Fixation of CO and the Strecker Reaction of Ketones.

A discrete tetrahedral indium cage, {[In(μ-OH)(HCO)(tcma)]} (In-GL), was synthesized solvothermally by the reaction of indium nitrate with the tripodal tricarboxylic acid ligand ,,-tris{(2'-carboxy[1,1'-biphenyl]-4-yl)methyl}methylammonium chloride ([Htcma]Cl). This cage consists of four trimeric units [In(μ-OH)(μ-CO)(μ-HCO)] and four [tcma] ligands, which all perform as 3-connection nodes to bridge each other, resulting in a tetrahedral cage structure. The trimeric unit [In(μ-OH)(μ-CO)(μ-HCO)] is observed for the first time in the family of In-based metal-organic structures and can be considered as an evolution of a 6-connected [In(μ-O)(μ-CO)] unit.

[Ag(N-triphos)(Cl)](NO): a stable Ag-P superatom with eight electrons (N-triphos = tris((diphenylphosphino)methyl)amine).

A first and stable Ag-P superatom nanocluster [Ag(N-triphos)(Cl)](NO) (1) has been successfully synthesized and characterized. X-ray analysis shows that this Ag cluster has a hexacapped body-centered cubic (bcc) framework which is consolidated by four tripodal N-triphos ligands. The identity of 1 is confirmed by high resolution ESI-MS.

Rare double spin canting antiferromagnetic behaviours in a [Co24] cluster.

A fish-basket-shaped [Co24] cluster, [Co24(μ3-O)4(ampc)4(μ3-OH)4(μ2-OH)4(NO3)5(HCO2)22(H2O)10]·[(HCO2)·2(CH3OH)·x(H2O)], was woven by bridging oxygen atoms from O(2-), OH(-), NO3(-) and HCO2(-) groups, and stabilized terminally by a semi-rigid organic ligand 4',4'-[(dimethylamino)dimethylene]-bis[(1,1'-biphenyl)-2-carboxylate] (ampc(-)). Magnetic analyses indicate that the [Co24] cluster exhibits two types of spin canting orders, spin flop and a small hysteresis with a coercive field of ca. 661 Oe and a remanent magnetization of 0.

Aggregation of the metallocycles {Cu8} and {Cu20} using [Cu(bp)] units (H2bp = bis(2-hydroxybenzyl)amine): structures and magnetic properties.

Two metallocycles, {Cu8(bp)4(OH)4(H2O)4(ClO4)4} (1) and {Cu20(bp)20} (2), were afforded by the reactions of the semi-flexible tridentate ligand bis(2-hydroxybenzyl)amine (H2bp) with Cu(ClO4)2·6H2O and Cu(OAc)2·H2O. Complex 1 has a saddle-shaped cyclic structure and complex 2 has a nanosized wheel-shaped structure. The two compounds consist of [Cu(bp)] units.

Nanospheric [M20(OH)12(maleate)12(Me2NH)12]4+ clusters (M = Co, Ni) with O(h) symmetry.

Nanospheric hydroxo-bridged clusters of [M(20)(OH)(12)(maleate)(12)(Me(2)NH)(12)](BF(4))(3)(OH)·nH(2)O (M = Co (1), Ni (2)) with O(h) symmetry were afforded under hydrothermal condition with Co(BF(4))(2)·6H(2)O/Ni(BF(4))(2)·6H(2)O and fumaric acid in a DMF/EtOH mixed solvent. They are characterized by elemental analysis, IR, and X-ray diffraction. X-ray single crystal diffraction analyses show that these two complexes are isostructural containing an ideally cubic M(8) core in that each two M atoms are doubly bridged at the edges by one OH(-) and one maleate, while these OH(-) and maleate groups are coordinated further by exterior identical 12 M atoms which construct a perfect M(12) icosahedron to encapsulate the cubic core.

Synthesis, structural characterization and luminescent properties of a series of Cu(I) complexes based on polyphosphine ligands.

A series of Cu(I) complexes with a [Cu(NN)(PP)](+) moiety, [Cu(phen)(pba)](BF(4)) (1a), [Cu(2)(phen)(2)(pbaa)](BF(4))(2) (2a), [Cu(2)(phen)(2)(pnaa)](BF(4))(2) (3a), [Cu(2)(phen)(2)(pbbaa)](BF(4))(2) (4a), [Cu(dmp)(pba)](BF(4)) (1b), [Cu(2)(dmp)(2)(pbaa)](BF(4))(2) (2b), [Cu(2)(dmp)(2)(pnaa)](BF(4))(2) (3b) and [Cu(2)(dmp)(2)(pbbaa)](BF(4))(2) (4b) (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, pba = N,N-bis((diphenylphosphino)methyl)benzenamine, pbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)benzene-1,4-diamine, pnaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)naphthalene-1,5-diamine and pbbaa = N,N,N',N'-tetrakis((diphenylphosphino)methyl)biphenyl-4,4'-diamine), were rationally designed and synthesized. These complexes were characterized by (1)H and (31)P NMR, electrospray mass spectrometry, elemental analysis and X-ray crystal structure analysis. Introduction of different central arene spacers (phenyl, naphthyl, biphenyl) into ligands, resulting in the size variation of these complexes, aims to tune the photophysical properties of the complexes.

A double-layered zinc(II) coordination polymer with the ligand 3,5-bis(carboxylatomethoxy)benzoate.

In the title compound, poly[hexaaquabis[mu(4)-3,5-bis(carboxylatomethoxy)benzoato]trizinc(II)], [Zn(3)(C(11)H(7)O(8))(2)(H(2)O)(6)](n), there are two crystallographically distinct Zn(II) cations which are bridged by polycarboxylate ligands in a mu(4)-bridging mode. A pair of ligands bridges adjacent Zn atoms to give centrosymmetric dimetal building blocks which act as four-connected nodes to be further interlinked into a two-dimensional double-layered framework with (4,4) topology. Other Zn atoms, lying on inversion centres, occupy the cavities of this topological structure.

μ-N,N,N',N'-Tetra-kis(diphenyl-phosphino-meth-yl)benzene-1,4-diamine-κP,P':P'',P''']bis-[bis-(nitrato-κO)palladium(II).

The asymmetric unit of the title complex, [Pd(2)(NO(3))(4)(C(58)H(52)N(2)P(4))], contains one half-mol-ecule, in which the central benzene ring is located on a crystallographic centre of inversion. The Pd atom has a distorted square-planar coordination consisting of two P and two O atoms. In the crystal structure, inter-molecular C-H⋯O inter-actions link the mol-ecules into chains, and π-π contacts between the phenyl rings [centroid-centroid distance = 3.

[μ-N,N'-Bis(diphenyl-phosphinometh-yl)benzene-1,4-diamine-κP:P']bis-[(2,2'-bipyridine-κN,N')silver(I)] bis-(per-chlorate) acetone disolvate.

The title complex, [Ag(2)(C(10)H(8)N(2))(2)(C(32)H(30)N(2)P(2))](ClO(4))(2)·2CH(3)COCH(3), is a centrosymmetric dimer with pairs of Ag(I) atoms bridged by N,N'-bis-(diphenyl-phosphinometh-yl)ben-zene-1,4-diamine ligands. In addition, each Ag(I) atom is coordin-ated by one chelating 2,2'-bipyridine ligand, giving a distorted trigonal coordination environment.

Bis[4-(2-hydroxy-benzyl-ideneamino)benzoato-κO]tetrakis-(methanol-κO)manganese(II).

In the title mononuclear complex, [Mn(C(14)H(10)NO(3))(2)(CH(3)OH)(4)], the Mn(II) atom, lying on an inversion centre, exhibits a distorted octa-hedral geometry, defined by two O atoms from two monodentate ligands and four O atoms from four methanol mol-ecules. The crystal structure involves intra-molecular O-H⋯N and O-H⋯O and inter-molecular O-H⋯O hydrogen bonds.

{μ-trans-N,N'-Bis[(diphenyl-phosphan-yl)meth-yl]benzene-1,4-diamine-κP:P'}bis-{(acetonitrile-κN)[dipyrido[3,2-a:2',3'-c]phenazine-κN,N]copper(I)} bis-(tetra-fluoridoborate).

In the centrosymmetric dinuclear title compound, [Cu(2)(C(2)H(3)N)(2)(C(18)H(10)N(4))(2)(C(32)H(30)N(2)P(2))](BF(4))(2), the Cu(I) centre is coordinated by two N atoms from a dipyridophenazine ligand, one P atom from an N,N'-bis-[(diphenyl-phosphan-yl)meth-yl]benzene-1,4-diamine (bpbda) ligand, and one N atom from an acetonitrile mol-ecule in a distorted tetra-hedral geometry. The bpbda ligand, lying on an inversion center, bridges two Cu(I) centres into a Z-shaped complex. Intra-molecular π-π inter-actions between the dipyridophenazine ligand and the benzene ring of the bpbda ligand are observed [centroid-centroid distance = 3.

A coordination polymer of CdCl2 with the novel zwitterionic dicarboxylate ligand 2,2'-(2-methylbenzimidazolium-1,3-diyl)diacetate (pda).

The title compound, poly[chlorido[mu(4)-2,2'-(2-methylbenzimidazolium-1,3-diyl)diacetato]cadmium(II)], [Cd(C(12)H(11)N(2)O(4))Cl](n), is an undulating two-dimensional polymer consisting of a paddlewheel Cd(2)(CO(2))(4) cluster which lies on an inversion centre. These paddlewheel clusters act as four-connected square building units interlinked via bridging zwitterionic dicarboxylate ligands into a corrugated layer which is consolidated by pi-pi interactions between benzene rings of benzimidazole groups. Neighbouring layers are further assembled via interlayer pi-pi interactions into a three-dimensional supramolecular structure.

catena-poly[[[pyridinecopper(II)]bis[mu3-4-(2-oxidobenzylideneamino)benzoato]] dimethylformamide disolvate], a polymer composed of dimeric dicopper building units.

The title compound, {[Cu(C(14)H(9)NO(3))(C(5)H(5)N)].C(3)H(7)NO}n or {[Cu(2)L(2)(py)(2)].2DMF}n [py is pyridine, L is 4-(salicylideneamino)benzoate and DMF is dimethylformamide], is composed of dimeric dicopper [CuL(py)]2 building units, which are interlinked into a one-dimensional chain through the formation of Cu-O(COO) bonds.