Sodium Copper Chlorophyllin Catalyzed Chemoselective Oxidation of Benzylic Alcohols and Diarylmethanes in Water.

We report the highly efficient and chemoselective oxidation of benzylic alcohols catalyzed by sodium copper chlorophyllin in water, producing corresponding arylcarbonyl compounds. Importantly, the catalytic system exhibits a wide substrate scope and high functional group tolerance. Moreover, secondary alcohols and even diarylmethanes were smoothly oxidized to the desired aryl ketones with excellent yields.

Syntheses, crystal structures, adsorption properties and visible photocatalytic activities of highly stable Pb-based coordination polymers constructed by 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline and bridging linkers.

Five highly stable coordination polymers assembled by 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (2-HNCP) and different aromatic carboxylic acid ligands, namely, [Pb(2-NCP)(L1)]n (1), [Pb2(2-NCP)2(L2)]n·2nH2O (2), [Pb2(2-NCP)2(L2)]n (3), [Pb(2-NCP)(L3)0.5]n (4) and [Pb2(2-NCP)2(L4)]n (5), where HL1 = pyridine-4-carboxylic acid, H2L2 = 2-amino-1,4-benzenedicarboxylic acid, H2L3 = 1,4-benzenedicarboxylic acid and H2L4 = 2-hydroxy-1,4-benzenedicarboxylic acid, have been synthesized under hydrothermal conditions. Their structures have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses and infrared spectroscopy. In 1, adjacent ladder-like chains are extended into a three-dimensional (3D) supramolecular architecture by π-π interactions. In 2, the neighboring layers are interconnected by π-π interactions to afford a 3D supramolecular architecture. 3-5 exhibit similar 3D frameworks with a Schläfli symbol of 412·63 topologies. The different auxiliary ligands and the pH value of the reaction system were discussed in regard to the formation of different structures. In addition, these five complexes present high thermal stabilities, the preferential adsorption of CO2 over N2 and excellent photocatalytic activities for dye degradation under visible light irradiation.

Highly Stable Copper(I)-Based Metal-Organic Framework Assembled with Resorcin[4]arene and Polyoxometalate for Efficient Heterogeneous Catalysis of Azide-Alkyne "Click" Reaction.

A new highly stable copper(I)-based metal-organic framework (MOF), namely, [CuI4(SiW12O40)(L)]·6H2O·2DMF (1), was synthesized by incorporating Keggin-type polyoxometalate (POM) anions and a functionalized wheel-like resorcin[4]arene-based ligand (L) under sovothermal condition. 1 exhibits a charming 3D supramolecular architecture sandwiched by the POM anions. Noticeably, 1 has exceptional chemical stability, especially in organic solvents or aqueous solutions with a wide range of pH values. Considering the catalytically active Cu(I) sites in 1, the azide-alkyne cycloaddition (AAC) reaction was studied by employing 1 as the heterogeneous catalyst. Most strikingly, 1 exhibits excellent catalytic activity as well as recyclability for the AAC reaction.

A multifunctional microporous metal-organic framework: efficient adsorption of iodine and column-chromatographic dye separation.

In this work, a multifunctional microporous metal-organic framework (MOF), [Cd(ABTC)(H2O)2(DMA)]·4DMA (JLNU-4; JLNU = Jilin Normal University; H4ABTC = 3,3',5,5'-azobenzenetetracarboxylic acid), has been synthesized based on the ligand H4ABTC under solvothermal conditions. JLNU-4 shows excellent uptake of iodine both in solution and in the vapor phase, owing to the existence of a microporous structure in JLNU-4. The adsorption kinetics during the process of iodine adsorption were analyzed via a series of qualitative and quantitative analyses, such as the Langmuir and Freündlich adsorption isotherms. In addition, according to UV/vis spectroscopy analysis and the colour variance of JLNU-4, the relatively small sized dye methylene blue (MB) could be efficiently adsorbed by JLNU-4, through size-exclusion effects. Particularly, JLNU-4 can serve as a column-chromatographic filler for the separation of dye molecules. Therefore, JLNU-4 is a multifunctional microporous MOF for iodine adsorption and column-chromatographic dye separation.

The Design of Dual-Emissive Composite Material [Zn2(HL)3]+@MOF-5 as Self-Calibrating Luminescent Sensors of Al3+ Ions and Monoethanolamine.

Introducing another chromophore into a luminescent MOF is a potential way to assembling novel dual-emissive luminescent materials. Putting the chromophore, for which luminescence can be enhanced by Zn2+ ion, into MOF-5 by the "bottle around ship" strategy is a simple but efficient synthesis method to realize such dual-emissive materials. According to this strategy, a novel dual-emissive luminescent composite material [Zn2(HL)3]+@MOF-5 was constructed by loading the [La3(HL)2L2(NO3)3H2O] (1) (H2L = 7,7'-(ethane-1,1'-diyl)8-hydro-quinoline) into MOF-5, in which the [Zn2(HL)3]+ anions were transformed from 1 with the existence of Zn2+. The dual-emissive composite materials show excellent luminescence with two emissions of MOF-5 at 410 nm and [Zn2(HL)3]+ at 524 nm. Furthermore, by combining characteristics of MOF-5 and the guest chromophore, the composite material is highly selectively sensitive toward Al3+ and monoethanolamine, which makes [Zn2(HL)3]+@MOF-5 a potential self-calibrated fluorescence sensor.

Poly[[tri-µ(3)-hydroxido-tris-(µ(4)-pyridine-2,5-dicarboxyl-ato)trineodymium(III)] monohydrate].

In the title compound, {[Nd(3)(C(7)H(3)NO(4))(3)(OH)(3)]·H(2)O}(n), the Nd(III) atom is eight-coordinated by the three O atoms of three asymmetrically µ(3)-bridging hydroxide groups, by four carboxyl-ate O atoms of four different pyridine-2,5-dicarboxyl-ate (2,5-pydc) ligands, and by the N atom of a 2,5-pydc ligand. Six Nd atoms are connected by six hydroxide groups, forming an [Nd(6)(µ(3)-OH)(6)] cluster unit of symmetry -3 and a slightly compressed octa-hedral geometry. Adjacent [Nd(6)(µ(3)-OH)(6)] clusters are connected by the 2,5-pydc ligands, via O and N atoms, forming chains along the c axis. The remaining O atoms of the 2,5-pydc ligands link these chains into a three-dimensional framework. A disordered water molecule, located on a threefold rotation axis at the opposite side of the [Nd(6)(µ(3)-OH)(6)] cluster and exposed to each of the three Nd atoms, completes the structure.

Bis(1,10-phenanthroline-5,6-dione-κN,N')silver(I) 2-hy-droxy-3,5-dinitro-benzoate.

In the cation of the title salt, [Ag(C(12)H(6)N(2)O(2))(2)](C(7)H(3)N(2)O(7)), the Ag(I) atom is coordinated in a distorted tetra-hedral geometry by four N atoms from two 1,10-phenanthroline-5,6-dione ligands, while the 3,5-dinitro-salicylate anion has only a short contact [2.847 (6) Å] between one of its O atoms and the Ag(I) atom. The dihedral angle between the two 1,10-phenanthroline-5,6-dione ligands is 58.4 (1)°. There is an intra-molecular O-H⋯O hydrogen bond in the 3,5-dinitro-salicylate anion.

2,4,5-Tris(pyridin-4-yl)-1H-imidazole monohydrate.

In the crystal structure of the title compound, C(18)H(13)N(5)·H(2)O, adjacent mol-ecules are linked by O-H⋯N and N-H⋯O hydrogen bonds, generating a chain propagating along [001].

Poly[[(µ-benzene-1,4-dicarboxyl-ato)bis-[µ-4-(1H-1,3,7,8-tetra-aza-cyclo-penta-[l]phenanthren-2-yl)benzoato]dizinc] tetra-hydrate].

In the title complex, [Zn(2)(C(8)H(4)O(4))(C(20)H(11)N(4)O(2))(2)]·4H(2)O, the Zn(II) atom is six-coordinated by two carboxyl-ate O atoms from one bidentate benzene-1,4-dicarboxyl-ate (1,4-BDC) ligand, two carboxyl-ate O atoms from two different monodentate 4-(1H-1,3,7,8-tetra-aza-cyclo-penta-[l]phenanthren-2-yl)benzoate (HNCP) ligands and two HNCP N atoms. The Zn(II) atoms are bridged by the centrosymmetric 1,4-BDC ligands, forming an extended single-chain structure. Neighbouring single chains are connected by the HNCP ligands from two opposite directions, resulting in a sheet. In addition, there are N-H⋯O hydrogen-bonding inter-actions between adjacent layers. As a result, the polymeric sheets are further extended into a three-dimensional supra-molecular structure.

Dichlorido(dipyrido[3,2-a:2',3'-c]phenazine)manganese(II).

The complete mol-ecule of the title compound, [MnCl(2)(C(18)H(10)N(4))(2)], is generated by crystallographic twofold symmetry with the Mn atom lying on the rotation axis. The Mn coordination geometry is a distorted cis-MnCl(2)N(4) octa-hedron, arising from two N,N'-bidentate dipyrido[3,2-a:2',3'-c]phenazine (DPPZ) ligands and two chloride ions. In the crystal structure, neighbouring mononuclear units pack together through π-π contacts between the DPPZ rings [shortest centroid-centroid distance = 3.480 (2) Å], leading to a chain-like structure along [001]. C-H⋯Cl hydrogen bonds complete the structure.

A one-dimensional chain structure based on unusual tetranuclear manganese(II) clusters.

The title coordination polymer, poly[bis(mu(4)-biphenyl-2,2'-dicarboxylato)(dipyrido[3,2-a:2',3'-c]phenazine)manganese(II)], [Mn(2)(C(14)H(8)O(4))(2)(C(18)H(10)N(4))](n), was obtained through the reaction of MnCl(2).4H(2)O, biphenyl-2,2'-dicarboxylic acid (H(2)dpdc) and dipyrido[3,2-a:2',3'-c]phenazine (L) under hydrothermal conditions. The asymmetric unit contains two crystallographically unique Mn(II) ions, one unique L ligand and two unique dpdc ligands. One Mn ion is six-coordinated by four O atoms from three different dpdc ligands and two N atoms from one L ligand, adopting a distorted octahedral coordination geometry. The distortions from ideal octahedral geometry are largely due to the presence of chelating ligands and the resulting acute N-Mn-N and O-Mn-O angles. The second Mn ion is coordinated in a distorted trigonal bipyramidal fashion by five O atoms from four distinct dpdc ligands. Four Mn(II) ions are bridged by the carboxylate groups of the dpdc ligands to form an unusual tetranuclear Mn(II) cluster. Clusters are further connected by the aromatic backbone of the dicarboxylate ligands, forming a one-dimensional chain structure along the b axis. The title compound is the first example of a chain structure based on a tetranuclear Mn(II) cluster.

catena-Poly[[aqua-(dipyrido[3,2-a:2',3'-c]phenazine-κN,N)iron(II)]-µ-pyrazine-2,3-dicarboxyl-ato-κN,O:O].

In the title compound, [Fe(C(6)H(2)N(2)O(4))(C(18)H(10)N(4))(H(2)O)](n), the Fe(II) ion adopts a slightly distorted octahedral mer-FeN(3)O(3) geometry, arising from one N,N'-bidentate dipyrido[3,2-a:2',3'-c]phenazine ligand, one N,O-chelating pyrazine-2,3-dicarboxyl-ate dianion and one water mol-ecule. An O-bonded symmetry-related dianion completes the coordination of the metal. The bridging dianion results in a one-dimensional polymeric chain. Aromatic π-π stacking inter-actions between ligands [centroid-centroid separations = 3.528 (2) and 3.741 (2) Å] and O-H⋯O and O-H⋯N hydrogen bonds link the chains together, leading to a three-dimensional supra-molecular network.

10,11,12,13-Tetrahydro-4,5,9,14-tetra-azadibenz[a,c]anthracene-benzene-1,4-dicarboxylic acid (2/1).

In the title adduct, 2C(18)H(14)N(4)·C(8)H(6)O(4), the centrosymmetric 1,4-benzene-dicarboxylic acid mol-ecule makes two O-H⋯·N hydrogen bonds to adjacent 10,11,12,13-tetra-hydro-4,5,9,14-tetra-azadibenzo[a,c]anthracene (TTBT) mol-ecules. Aromatic π-π stacking inter-actions occur between TTBT rings [centroid-centroid distance = 3.570 (3) Å], leading to a two-dimensional supra-molecular structure in the crystal.

catena-Poly[[aqua-(pyrazino[2,3-f][1,10]phenanthroline-κN,N)cobalt(II)]-µ-pyrazine-2,3-dicarboxyl-ato-κNO:O].

In the title compound, [Co(C(6)H(2)N(2)O(4))(C(14)H(8)N(4))(H(2)O)](n), the Co atom is bonded to one N,N'-bidentate pyrazino[2,3-f][1,10]phenanthroline (Pyphen) ligand, one N,O-bidentate pyrazine-2,3-dicarboxyl-ate (PZDC) dianion and one water mol-ecule in a distorted octa-hedral mer-CoN(3)O(3) geometry. The Co(II) atoms are bridged by the PZDC dianions, forming an infinite one-dimensional chain running along the b axis. Adjacent chains pack together through π-π stacking inter-actions [centroid-centroid separations = 3.498 (4) and 3.528 (4) Å], and O-H⋯O and O-H⋯N hydrogen bonds involving the water mol-ecule complete the structure.

catena-Poly[[aqua-(dipyrido[3,2-a:2',3'-c]phenazine-κN,N)zinc(II)]-µ-pyrazine-2,3-dicarboxyl-ato-κN,O:O].

In the title compound, [Zn(C(6)H(2)N(2)O(4))(C(18)H(10)N(4))(H(2)O)](n) or [Zn(PZDC)(DPPZ)(H(2)O)](n) (where DPPZ is dipyrido[3,2-a:2',3'-c]phenazine and H(2)PZDC is pyrazine-2,3-dicarboxylic acid), the Zn atom is six-coordinated in a slightly distorted octa-hedral coordination geometry by three N atoms from one DPPZ ligand and one PZDC(2-) dianion, three O atoms from two different PZDC(2-) ligands and one water mol-ecule. Each PZDC(2-) dianion serves as a spacer, connecting adjacent metal atoms into a polymeric chain structure parallel to the b axis. The chain motif is consolidated into a three-dimensional supra-molecular network by O-H⋯O and O-H⋯N hydrogen bonds and π-π aromatic stacking inter-actions involving adjacent DPPZ ligands and PZDC(2-) dianions with centroid-centroid separations of 3.522 (6) and 3.732 (8) Å, respectively.

Bis[3,5-difluoro-2-(2-pyrid-yl)phen-yl](picolinato)iridium(III).

The Ir centre in the title complex, [Ir(C(11)H(6)F(2)N)(2)(C(6)H(4)NO(2))], is six-coordinated in a slightly distorted octa-hedral IrC(2)N(3)O fashion.

Dichlorido(10,11,12,13-tetra-hydro-4,5,9,14-tetra-azabenzo[b]triphenyl-ene)cadmium(II) hemihydrate.

In the title compound, [CdCl(2)(C(18)H(14)N(4))(2)]·0.5H(2)O, the Cd atom assumes a distorted octa-hedral trans-CdCl(2)N(4) geometry arising from its coordination by two N,N'-bidentate 10,11,12,13-tetra-hydro-4,5,9,14-tetra-azabenzo[b]triphenyl-ene (TBBT) mol-ecules and two chloride ions. In the crystal, π-π aromatic stacking inter-actions between adjacent TTBT rings are seen, with a centroid-centroid distance of 3.604 (3) Å. An O-H⋯Cl hydrogen bond between the half-occupied water molecule and one chloride ion also occurs.

Bis(imidazo[4,5-f][1,10]phenanthroline)dinitratolead(II).

In the title compound, [Pb(NO(3))(2)(C(13)H(8)N(4))(2)], the Pb(II) atom (site symmetry 2) is hexa-coordinated by four N atoms from two N,N'-bidentate imidazo[4,5-f][1,10]phenanthroline (L) ligands and two O atoms from two weakly coordinated nitrate ions [Pb-O = 2.872 (5) Å] in an irregular arrangement, which may be ascribed to the stereochemically active lone pair of electrons on the metal ion. In the crystal, inter-molecular bifurcated N-H⋯(O,O) hydrogen bonds connect the mol-ecules into chains propagating along [100]. Adjacent chains inter-act by strong aromatic π-π stacking inter-actions, with a centroid-centroid distance of 3.483 (2) Å.