Novel Lanthanide (III) Complexes Derived from an Imidazole–Biphenyl–Carboxylate Ligand: Synthesis, Structure and Luminescence Properties

A series of neutral mononuclear lanthanide complexes [Ln(HL)2(NO3)3] (Ln = La, Ce, Nd, Eu, Gd, Dy, Ho) with rigid bidentate ligand, HL (4′-(1H-imidazol-1-yl)biphenyl-4-carboxylic acid) were synthesized under solvothermal conditions. The coordination compounds have been characterized by infrared spectroscopy, thermogravimetry, powder X-ray diffraction and elemental analysis. According to X-ray diffraction, all the complexes are a series of isostructural compounds crystallized in the P2/n monoclinic space group. Additionally, solid-state luminescence measurements of all complexes show that [Eu(HL)2(NO3)3] complex displays the characteristic emission peaks of Eu(III) ion at 593, 597, 615, and 651 nm.

Multifunctional Viologen-Derived Supramolecular Network with Photo/Vapochromic and Proton Conduction Properties

A supramolecular network [H4bdcbpy(NO3)2·H2O] (H4bdcbpy = 1,1′-Bis(3,5-dicarboxybenzyl)-4,4′-bipyridinium) (1) was prepared by a zwitterionic viologen carboxylate ligand in hydrothermal synthesis conditions. The as-synthesized (1) has been well characterized by means of single-crystal/powder X-ray diffraction, elemental analysis, thermogravimetric analysis and infrared and UV-vis spectroscopy. This compound possesses a three-dimensional supramolecular structure, formed by the hydrogen bond and π–π interaction between the organic ligands. This compound shows photochromic properties under UV light, as well as vapochromic behavior upon exposure to volatile amines and ammonia, in which the electron transfer from electron-rich parts to the electron-deficient viologen unit gives rise to colored radicals. Moreover, the intensive intermolecular H-bonding networks in 1 endows it with a proton conductivity of 1.06 × 10−3 S cm−1 in water at 90 °C.

A cobalt-based coordination polymer with a tripodal carboxylate ligand: synthese, structure and properties

A new cobalt-based coordination polymer (CP), [Co(Htatb)(1,4-bib)]·DMF (1), has been hydrothermally synthesized from CoCl2 ·6H2O, 4,4′,4′′-s-triazine-2,4,6-tribenzoic acid (H3tatb), and 1,4-bis(1-imidazoly)benzene (1,4-bib). The product has been characterized by IR spectroscopy, elemental and thermogravimetric analysis, and single-crystal X-ray diffraction. In compound 1, the Htatb ligand links three CoII ions resulting in a double-strand chain structure, further bridged through the 1,4-bib ligands to generate a 2D structure with channels. The fluorescence and cyclovoltammetry characteristics of compound 1 have also been investigated.

Structure-guided insights into heterocyclic ring-cleavage catalysis of the non-heme Fe (II) dioxygenase NicX

Biodegradation of aromatic and heterocyclic compounds requires an oxidative ring cleavage enzymatic step. Extensive biochemical research has yielded mechanistic insights about catabolism of aromatic substrates; yet much less is known about the reaction mechanisms underlying the cleavage of heterocyclic compounds such as pyridine-ring-containing ones like 2,5-hydroxy-pyridine (DHP). 2,5-Dihydroxypyridine dioxygenase (NicX) from Pseudomonas putida KT2440 uses a mononuclear nonheme Fe(II) to catalyze the oxidative pyridine ring cleavage reaction by transforming DHP into N-formylmaleamic acid (NFM). Herein, we report a crystal structure for the resting form of NicX, as well as a complex structure wherein DHP and NFM are trapped in different subunits. The resting state structure displays an octahedral coordination for Fe(II) with two histidine residues (His265 and His318), a serine residue (Ser302), a carboxylate ligand (Asp320), and two water molecules. DHP does not bind as a ligand to Fe(II), yet its interactions with Leu104 and His105 function to guide and stabilize the substrate to the appropriate position to initiate the reaction. Additionally, combined structural and computational analyses lend support to an apical dioxygen catalytic mechanism. Our study thus deepens understanding of non-heme Fe(II) dioxygenases.

A copper complex of an unusual hydroxy–carboxylate ligand: [Cu(bpy)(C4H4O6)]

A copper(II) complex, (2,2′-bipyridine-κ2 N,N′)[2-hydroxy-2-(hydroxymethyl-κO)propanedioato-κ2 O 1,O 3]copper(II), [Cu(C4H4O6)(C10H8N2)], containing the unusual anionic chelating ligand 2-(hydroxymethyl)tartronate, has been synthesized. [Cu(bpy)2(NO3)](NO3) was mixed with ascorbic acid and Dabco (1,4-diazabicyclo[2.2.2]octane) in DMF (dimethylformamide) solution in the presence of air to produce the title compound. The structure consists of square-pyramidal complexes that are joined by Cu...O contacts [2.703 (2) Å] into centrosymmetric dimers. The C4H4O6 2− ligand, which occupies three coordination sites at Cu, has previously been identified as an oxidation product of ascorbate ion.

Pyrene Carboxylate Ligand Based Coordination Polymers for Microwave-Assisted Solvent-Free Cyanosilylation of Aldehydes

The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) (2) are reported, being prepared by the solvothermal reactions of 5-{(pyren-4-ylmethyl)amino}isophthalic acid (H2L) with Zn(NO3)2.6H2O or Cd(NO3)2.4H2O, respectively. They were synthesized in a basic ethanolic medium or a DMF:H2O mixture, respectively. These compounds were characterized by single-crystal X-ray diffraction, FTIR spectroscopy, thermogravimetric and elemental analysis. The single-crystal X-ray diffraction analysis revealed that compound 1 is a one dimensional linear coordination polymer, whereas 2 presents a two dimensional network. In both compounds, the coordinating ligand (L2−) is twisted due to the rotation of the pyrene ring around the CH2-NH bond. In compound 1, the Zn(II) metal ion has a tetrahedral geometry, whereas, in 2, the dinuclear [Cd2(COO)2] moiety acts as a secondary building unit and the Cd(II) ion possesses a distorted octahedral geometry. Recently, several CPs have been explored for the cyanosilylation reaction under conventional conditions, but microwave-assisted cyanosilylation of aldehydes catalyzed by CPs has not yet been well studied. Thus, we have tested the solvent-free microwave-assisted cyanosilylation reactions of different aldehydes, with trimethylsilyl cyanide, using our synthesized compounds, which behave as highly active heterogeneous catalysts. The coordination polymer 1 is more effective than 2, conceivably due to the higher Lewis acidity of the Zn(II) than the Cd(II) center and to a higher accessibility of the metal centers in the former framework. We have also checked the heterogeneity and recyclability of these coordination polymers, showing that they remain active at least after four recyclings.

Structure and assembly of the diiron cofactor in the heme-oxygenase–like domain of the N-nitrosourea–producing enzyme SznF

In biosynthesis of the pancreatic cancer drug streptozotocin, the tridomain nonheme-iron oxygenase SznF hydroxylates Nδ and Nω′ of Nω-methyl-l-arginine before oxidatively rearranging the triply modified guanidine to the N-methyl-N-nitrosourea pharmacophore. A previously published structure visualized the monoiron cofactor in the enzyme’s C-terminal cupin domain, which promotes the final rearrangement, but exhibited disorder and minimal metal occupancy in the site of the proposed diiron cofactor in the N-hydroxylating heme-oxygenase–like (HO-like) central domain. We leveraged our recent observation that the N-oxygenating µ-peroxodiiron(III/III) intermediate can form in the HO-like domain after the apo protein self-assembles its diiron(II/II) cofactor to solve structures of SznF with both of its iron cofactors bound. These structures of a biochemically validated member of the emerging heme-oxygenase–like diiron oxidase and oxygenase (HDO) superfamily with intact diiron cofactor reveal both the large-scale conformational change required to assemble the O2-reactive Fe2(II/II) complex and the structural basis for cofactor instability—a trait shared by the other validated HDOs. During cofactor (dis)assembly, a ligand-harboring core helix dynamically (un)folds. The diiron cofactor also coordinates an unanticipated Glu ligand contributed by an auxiliary helix implicated in substrate binding by docking and molecular dynamics simulations. The additional carboxylate ligand is conserved in another N-oxygenating HDO but not in two HDOs that cleave carbon–hydrogen and carbon–carbon bonds to install olefins. Among ∼9,600 sequences identified bioinformatically as members of the emerging HDO superfamily, ∼25% conserve this additional carboxylate residue and are thus tentatively assigned as N-oxygenases.