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.

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].

Preparation of Rhodium(III) complexes with 2(1H)-quinolinone derivatives and evaluation of their in vitro and in vivo antitumor activity.

A series of 2(1H)-quinolinone derivatives and their rhodium (III) complexes were designed and synthesized. All the rhodium (III) complexes exhibited higher in vitro cytotoxicity for Hep G2, HeLa 229, MGC80-3, and NCI-H460 human tumor cell lines than their ligands and cisplatin, and among them complex 9 was found to be selectively cytotoxic to tumor cells. Further investigation revealed that complex 9 caused cell cycle arrest at the G2/M phase and induced apoptosis, and inhibited the proliferation of Hep G2 cells by impeding the phosphorylation of epidermal growth factor receptor (EGFR) and its downstream enzymes.

[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.

Counter-anion role in the formation of two supramolecular complexes: [Ag2(DPP)2](ClO4)2·CH3CN and [Ag2(DPP)2(NO3)2] {DPP is N-[(diphenylphosphanyl)methyl]pyridin-4-amine}.

The title compounds, bis{μ-N-[(diphenylphosphanyl)methyl]pyridin-4-amine-κ(2)N(1):P}disilver bis(perchlorate) acetonitrile monosolvate, [Ag2(C18H17N2P)2](ClO4)2·CH3CN, (1), and bis{μ-N-[(diphenylphosphanyl)methyl]pyridin-4-amine-κ(2)N(1):P}bis[(nitrato-κ(2)O,O)silver], [Ag2(C18H17N2P)2(NO3)2], (2), each contain disilver macrocyclic [Ag2(C18H17N2P)2](2+) cations lying about inversion centres. The cations are constructed by two N-[(diphenylphosphanyl)methyl]pyridin-4-amine (DPP) ligands linking two Ag(+) cations in a head-to-tail fashion. In (1), the unique Ag(+) cation has a near-linear coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands.

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.

Bis{N,N-bis-[(diphenyl-phosphan-yl)meth-yl]aniline-κP,P'}copper(I) tetra-fluoridoborate.

In the cation of the title compound, [Cu(C(32)H(29)NP(2))(2)]BF(4), the Cu(I) atom is four-coordinated in a distorted tetra-hedral geometry by four P atoms from two N,N-bis-[(diphenyl-phosphan-yl)meth-yl]aniline ligands. In the crystal, the cations are linked by C-H⋯π inter-actions, forming chains along the a axis. Intra-molecular C-H⋯N and inter-molecular C-H⋯F hydrogen bonds are also observed.

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'-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.

Tetra-aqua-bis(2-methyl-benzimidazolium-1,3-diacetato-κO)zinc(II) tetra-hydrate.

The asymmetric unit of the title compound, [Zn(C(12)H(11)N(2)O(4))(2)(H(2)O)(4)]·4H(2)O, contains one-half of the complex mol-ecule and two uncoordin-ated water mol-ecules. The four water O atoms in the equatorial plane around the Zn(II) centre ( symmetry) form a distorted square-planar arrangement, while the distorted octa-hedral coordination geometry is completed by the O atoms of the zwitterionic 2-methyl-benzimidazolium-1,3-diacetate ligands in the axial positions. The benzimidazole ring system is planar, with a maximum deviation of 0.

{4-[(Diphenyl-phosphino)methyl-amino]pyridinium-κP}bis-(nitrato-κO)silver(I).

In the title mononuclear complex, [Ag(C(18)H(18)N(2)P)(NO(3))(2)], the metal centre is coordinated in a slightly distorted trigonal-planar geometry by the P atom of the phosphine ligand and the O atoms of the two monodentate nitrate anions. In the crystal structure, complex mol-ecules are connected by inter-molecular N-H⋯O hydrogen bonds, forming chains running parallel to the b axis.

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.