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Vol 42, No 3 (2016)
- Year: 2016
- Articles: 10
- URL: https://journals.rcsi.science/1070-3284/issue/view/13282
Article
Crystal structures of the polymer copper(II) complexes with acylhydrazones of bromosalicylaldehyde derivatives
Abstract
Polymer copper(II) complexes with 5-bromosalicylaldehyde heptanoylhydrazone (I) and 3,5-dibromosalicylaldehyde acetylhydrazone (II) are synthesized and structurally characterized. In complex I, the formation of the polymer is due to the coordination of the hydrazide nitrogen atom to the copper(II) ion of the adjacent fragment. In complex II, polymer formation is due to the binding of the monomer fragments by dipyridyl linkers (CIF files CCDC 947908 (I) and 947909 (II)).
151-156
Mono- and dinuclear vanadium complexes with the pentadentate schiff base 2,6-diacetylpyridine bis(nicotinylhydrazone): Synthesis and structures
Abstract
A reaction between VOSO4, 2,6-diacetylpyridine, and nicotinohydrazide in a molar ratio of 1: 1: 2 afforded two complexes differing in both color and crystal shape as well as in chemical composition and molecular structure. The compositions and structures of the vanadium complexes were determined by IR spectroscopy and X-ray diffraction (CIF files CCDCnos. 1411235 (I) and 1411236 (II)). These complexes can be formulated as [V2II(H2L)2](NO3)4 ∙ H2O (I) and [VIV(=O)(H2L)(SO4)] ∙ 5H2O (II), where H2L is 2,6-diacetylpyridine bis(nicotinylhydrazone). Complex I consists of centrosymmetric dinuclear complex cations [V2(H2L)2]4+, NO3- anions, and crystal water molecules in a ratio of 1: 4: 1; complex II is built from molecular V(IV) complexes and crystal water molecules in a ratio of 1: 5. The coordination polyhedron of the metal atom in I is a tetragonal pyramid made up of the electron-donating atoms N3O2 of two ligands H2L. The coordination polyhedron of the metal atom in II is a pentagonal bipyramid made up of the electron-donating atoms N3O2 of one neutral five-coordinate ligand H2L and two O atoms coming from the oxo ligand and the SO42- anion coordinated in a monodentate fashion.
157-165
Synthesis, characterization, and structure of a new ferromagnetically coupled tetranuclear nickel cubane complex
Abstract
A new nickel complexes [Ni(L)4(OCH3)4(CH3OH)4] (I) (HL = salicylaldehyde) was synthesized and structurally characterized by elemental analyses and single-crystal X-ray diffraction (CIF file CCDC no. 1410887). The complex crystallizes in monoclinic P21/c space group and consists of one crystallographically independent molecule which contains a distorted tetranuclear cubane core with alternating nickel and oxygen atoms of the four on the corners. The magnetic properties reveal the presence of ferromagnetic interactions between the nickel(II) centers in the cubic cluster with two different exchange pathways.
166-169
Synthesis and structural characterization of two new copper(II) complexes with 3-oxapentane-1,5-diamine using different molar ratio
Abstract
The reactions of copper(II) nitrate with 3-oxapentane-1,5-diamine (Oda) were investigated under different molar ratio. In the case of a 1: 1 molar ratio of copper(II) nitrate and Oda, the mononuclear complex [Cu(Oda)(NO3)2] (I) was obtained. In contrast, the treatment of copper(II) nitrate with twice Oda afforded inorganic polymer {[Cu(μ-Oda)(Oda)] · (NO3)2}n (II). The molecular structures of the two new complexes were determined from the elemental analyses, IR spectra and single-crystal X-ray diffraction (CIF files CCDC nos. 828193 (I) and 828018 (II)). Two Cu(II) complexes were both five-coordinated and forming a distorted square-base pyramidal geometry. Two complexes are stabilized by the intermolecular hydrogenbond.
170-177
Complexes of Ir(III) and Pt(II) with cyclometallated 2-phenylbenzothiazole and chelating diethyldithiocarbamate and O-ethyldithiocarbonate ions: Structures and optical and electrochemical properties
Abstract
It is shown by X-ray diffraction analysis, IR spectroscopy, and 1Н, 13С{1H}, and 195Pt NMR spectroscopy that the Pt(II) and octahedral Ir(III) complexes with metallated 2-phenylbenzothiazole and chelating diethyldithiocarbamate and O-ethyldithiocarbonate ions have the square and cis-C,C structure, respectively. The highest occupied and lowest unoccupied molecular orbitals of the complexes determining their long-wavelength absorption, phosphorescence, and one-electron oxidation and reduction are assigned to those predominantly localized on the mixed p(S)/d(M) and π* orbitals of the metallated ligand. The cathodic shift of the oxidation voltammogram and the bathochromic phosphorescence shift of the Pt(II) complex with the О-ethyldithiocarbonate ion are attributed to the enhanced donor–acceptor interaction of the donor S atoms of the ligand with Pt(II). The structural data are deposited with the Cambridge Crystallographic Data Centre (CIF files CCDC nos. 1058768 (Ia) and 1058767 (IIb)).
178-186
Cyclometallated iridium(III) complex with 2-(benzo[b]thiophen-2-yl)pyridyl and norbornene-substituted pyrazolonate ligands and related electroluminescent red light-emitting polymers
Abstract
New cyclometallated iridium(III) complex, (NBEpz)Ir(Btp)2 (I) (NBEpzH is 1-phenyl-3-methyl-4-(5-bicyclo[2.2.1]hept-5-en-2-yl)-5-pyrazolone, and BtpH is 2-(benzo[b]thiophen-2-yl)pyridine), is synthesized. The structure of the compound is determined by X-ray diffraction analysis (CIF file CCDC no. 1406737). Copolymers with the carbazole and iridium-containing fragments in the side chains (P1–P3) are prepared from monomer I using the ROMP method (ROMP is Ring-Opening Metathesis Polymerization). Their photoluminescence and electroluminescence properties are studied. Copolymers P1–P3 exhibit an intense photoluminescence and electroluminescence of red color. The maximum current efficiency (17.9 cd/A) and power efficiency (9.1 lm/W) are reached using emitter P2.
187-195
Cluster [Re3S5(Dppe)3]+ and its oxidation to [Re3S4(SO2)(Dppe)3]+
Abstract
The reaction of cluster [Re3S4(Dppe)3Br3]Br with sodium tert-butyl thiolate affords trinuclear cationic cluster [Re3S5(Dppe)3]Br (I). The oxidation of cluster I with air gives [Re3S4(SO2)(Dppe)3]Cl (II), which is characterized by X-ray diffraction analysis in the form of solvate II · 3.5CH2Cl2 (CIF file CCDC 1401732). The DFT calculations indicate the triplet ground state of the [Re3S5(Dppe)3]+ cation and a significant spin density on the equatorial sulfide ligands, favoring the oxidation of the cluster.
196-200
Synthesis and structure of osmium complexes: [Ph4Sb]2+ [OsCl6]2–, and [p-Tol4Sb]2+[OsCl6]2—
Abstract
The reaction of sodium hexachloroosmate with tetraphenyl- or tetra(para-tolyl)stibonium chloride in dimethyl sulfoxide gave the complexes [Ph4Sb]2[OsCl6] (I) and [p-Tol4Sb]2[OsCl6] (II). According to X-ray diffraction data, the CSbC angles in the tetrahedral cations [Ph4Sb]+ and [p-Tol4Sb]+ are 105.97(17)°–117.98(16)° in I and 103.1(3)°–118.0(2)° in II; the Sb–C bond lengths vary in the ranges of 2.090(4)–2.104(4) Å (I) and 2.086(6)–2.107(7) Å (II). In the octahedral anions [OsCl6]2–, the Os–Cl bond lengths are 2.3364(10)–2.3435(12) Å (I) and 2.3159(16)–2.3361(19) Å (II) (CIF files CCDC no. 1000137 (I), 1010809 (II)).
201-206
Synthesis and structural determination of mononuclear eight-coordinate (EnH)[LuIII(Egta)] · 2H2O and 2D ladder-like nine-coordinate (EnH2)[YIII(Egta)(H2O)]2 · 6H2O
Abstract
Two novel lanthanide complexes, (EnH)[LuIII(Egta)] · 2H2O (I) and (EnH2)[YIII(Egta)H2O]2 · 6H2O (II), where En = ethylenediamine and H4Egta = ethyleneglycol-bis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, have been successfully synthesized through direct heating reflux and their molecular crystal structures were determined by FT-IR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques (CIF files CCDC nos. 966211 (I) and 966210 (II)). X-ray diffraction reveals that I has a eight-coordinate mononuclear structure with distorted square antiprismatic conformation. The reason that the Lu(III) adopts a eight-coordinate conformation is the small ionic radius and more f-orbital electrons, which generates a relatively small coordination number. Complex I crystallizes in a orthorhombic system with Pca21 space group. The crystal data are as follows: a = 22.4933(14), b = 9.1067(7), c = 10.6450(5) Å and V = 2180.5(2) Å3. Complex II takes nine-coordinated structure with a monocapped square antiprism, and crystallizing in the monoclinic crystal system with P21/c space group. The cell dimensions are as follows: a = 12.9600(11), b = 12.6209(12), c = 16.9151(15) Å, β = 122.021(2)° and V = 2345.8(4) Å3. Each ethylenediammonium (EnH22+) cation in (EnH2)[YIII(Egta)H2O]2 · 6H2O (II) connects three adjacent [YIII(Egta)(H2O)]22- anions through hydrogen bonds. While in II, there are two types of EnH22+ cations, which form hydrogen bonds with the neighboring [YIII(Egta)(H2O)]22- anions, leading to the formation of a 2D ladder-like layer structure. The results showed that the ionic radius of rare earth metals play a crucial role in crystal and molecular structure of their complexes.
207-216
Syntheses and luminescence of four supramolecular coordination complexes with flexible ligand
Abstract
Four d10-based complexes with chemical formulae {[Zn(L1)2(H2O)2(4,4′-Bipy)2] (I), {[Zn2(L1)4(Mi)] · 4H2O} (II), {[Zn(L1)2(Phen)] · H2O} (III) {[Cd(L1)2(Phen)] · 2H2O} (IV) (HL1 = p-hydroxy phenylacetic acid, 4,4′-Bipy = 4,4′-bipyridine, Phen = 1,10-phenanthroline, Mi = 1,4-bis(imidazol-1-yl)butane) have been synthesized and structurally characterized by single crystal X-ray diffraction (CIF files CCDC nos. 1047119 (I), 1047120 (II), 1047121 (III), 1047122 (IV)). The significant effect of assistant ligands and metal ions on assembly of I‒IV has been demonstrated, which leads to the formation of distinct crystalline products. Complexes I‒IV show various coordination motifs with different existing forms and coordination modes of the organic ligands. Furthermore, extend supramolecular networks are connected by secondary interactions such as hydrogen-bonding and aromatic stacking. The thermal stability and luminescent properties of the compounds were discussed in detail.
217-224