Shan-Shan Zhang

Synthesis, characterization and luminescence properties of Eu(III) and Tb(III) complexes with novel pyrazole derivatives and 1,10-phenanthroline.

Two novel pyrazole-derived ligands, 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid (CDPA) and 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)-N-phenylpicolinamide (CDPP) were prepared by 3,6-dichloropicolinic acid (DCPA). Their complexes with terbium(III) and europium(III) were synthesized. The complexes were characterized by elemental analysis, infrared spectra, (1)H NMR and TG-DTG. Furthermore, the above complexes using 1,10-phenanthroline as a secondary ligand were also synthesized and characterized. The luminescence properties of these complexes in solid state were investigated. The results suggested that Tb(III) complexes exhibit more efficient luminescence than Eu(III) complexes and the fluorescence of the complexes with 1,10-phenanthroline as a secondary ligand was prominently stronger than that of complexes without this ligand., and the three ligand (DCPA), (CDPP) and (CDPA) are excellent sensitizers to Eu(III) and Tb(III) ion.

Synthesis and crystal structures of supramolecular compounds: [Cu(mpca)2(H2O)] · 3H2O and [Cu2(mpca)2(pyr)4]

A new chelate ligand, 5-methyl-1H-pyrazole-3-carboxylic acid (mpca), has been synthesized. This ligand reacts with cupric sulfate to give two supramolecular compounds [Cu(mpca)2(H2O)] · 3H2O (1) and [Cu2(mpca)2(pyr)4] (Pyr = pyridine) (2), which were characterized by elemental analysis and X-ray crystal diffraction. Helical water chain and strong π–π interaction are important for the stability of the 3-D structure of these supramolecules.

Synthesis, Structure, Thermal and Fluorescent Properties of a Novel Mn(II) Coordination Polymer and its Hexacyclic Water Ring

A novel Imazethapyr-bridged complex [Mn(Ima)2] (H2O)2 (1) [Imazethapyr (Ima)=5-ethyl-2-(5-isopropyl-5-methyl-4-oxo-4,5-dihydro-1H-imidazol-2-yl) nicotinic acid, has been synthesized and structurally characterized by X-ray diffraction method, infrared spectra, elemental analysis and thermal analysis. The title polymer contains a monocyclic hexamer water cluster, and the cluster plays an important role in stabilizing the complex. The fluorescence of the complex 1 in the solid state was investigated via FL55 spectrophotometer and it indicated a fluorescent behavior at room temperature.Graphical AbstractA novel Imazethapyr-bridged complex [Mn(Ima)2] (H2O)2 [Imazethapyr (Ima) = 5-ethyl-2-(5-isopropyl-5-methyl-4-oxo-4,5-dihydro -1H-imidazol-2-yl) nicotinic acid, has been synthesized and structurally characterized by X-ray diffraction method, infrared spectra, elemental analysis and thermal analysis. The title polymer contains a monocyclic hexamer water cluster, and the cluster plays an important role in stabilizing the complex.

3‐Chloro‐6‐(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)picolinic acid

In the title compound, C11H10ClN3O2, the dihedral angle between the two rings is 5.6°. The crystal structure is stabilized by O—H⋯O hydrogen bonds.

Crystal structure of bis[2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol]-bis[5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinato]manganese(II), Mn(C13H12F2N6O)2(C15H18N3O3)2

C56H60F4MnN18O8, triclinic, P1 (no. 2), a = 9.7450(6) Å, b = 11.2747(6) Å, c = 15.2325(8) Å, + = 79.072(4)°, ) = 78.248(4)°, & = 65.073(3)°, V = 1475.7 Å, Z = 1, Rgt(F) = 0.048, wRref(F) = 0.139, T = 296 K. Source of material An ethanol solution of 2-(2,4-difluorophenyl)-1,3-bis(1,2,4triazol-1-yl)propan-2-ol (Fluconazole, HFlu, 0.05 mmol) and 5ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid (Imazethapyr, Imaz, 0.05 mmol) were added to a solution of manganese chloride (0.2 mmol) in water (10 ml). Then a purple solution was obtained. The crystals were obtained by evaporating the solution at room temperature for several days. Elemental analysis — found: C, 53.79 %; H, 5.16 %; N, 20.26 %; calculated for C56H60F4MnN18O8: C, 53.84 %; H, 5.13 %; N, 20.19 %. Experimental details The isopropyl, methyl, N12 and O5 of the imidazole ring of the Imaz are disordered with occupancy of 0.5/0.5. Discussion 2-(2,4-Difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol (HFlu) is one of the first-line popular drugs used to treat invasive infections [1]. 5-Ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid (IMaz) is an imidazole compound used as a selective herbicide [2]. Both of them would be an interesting candidate to construct coordination polymers, since it combines the features required for coordination to metal ions through nitrogen atoms and oxygen atoms for extended intermolecular interactions. Thus, the HFlu and Imaz ligands are potential to construct a diversity of coordination architectures upon the metal complexation. The crystal structure of the title complex consists of divalent manganese cation coordinated by six N atoms. Two N atoms originate from two triazole of two different HFlu molecules and the other four N atoms are from two different imazethapyr anions (two N atoms from two pyridyl rings and the other two N atoms from two oxo-imidazole rings). The lengths of Ni—N bonds are in the range of 2.220(2) 2.304(1) Å. The associated angles range from 71.54(5)° to 180.00(5)°. It indicates that manganese(II) has a distorted octahedral coordination. The pyridinyl ring C2–C3–C4–C5–C6–N3 and the triazole ring N2–C17–N9– Z. Kristallogr. NCS 225 (2010) 213-215 / DOI 10.1524/ncrs.2010.0092 213

Diaqua-(5-methyl-1H-pyrazole-3-carboxyl-ato)(4-nitro-benzoato)copper(II).

In the title complex, [Cu(C7H4NO4)(C5H5N2O2)(H2O)2], the CuII ion is coordinated in a slightly distorted square-pyramidal enviroment. The basal plane is formed by an N atom and an O atom from a 5-methyl-1H-pyrazole-3-carboxylate ligand and by two O atoms from two water ligands. The apical position is occupied by a carboxylate O atom from a 4-nitrobenzoate ligand. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link complex moleclues, forming extended chains parallel to the a axis.

3,6-Dichloro-N-(4,6-dichloro­pyrimidin-2-yl)picolinamide

In the title compound, C10H4Cl4N4O, the pyridine and pyrimidine rings are nearly perpendicular to each other, the dihedral angle between them being 86.60 (10)°. In the crystal structure, the N and O atoms in the amide group are involved in intermolecular hydrogen bonds, forming a one-dimensional chain along the c axis.

3-Chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid-triphenyl-phosphine oxide (1/1).

In the title 1:1 adduct, C11H10ClN3O2·C18H15OP, the dihedral angle between the pyridine and pyrazole rings is 10.3 (2)°. The two components of the adduct are linked by an O—H⋯O hydrogen bond.