Syntheses, crystal structures, and magnetic properties of metal-organic hybrid materials of Mn(II)/Co(II): three-fold interpenetrated alpha-polonium-like network in one of them

Three new 1,4-phenylenediacrylate bridged Mn(II) and Co(II) complexes of molecular formulas {[Mn2(ppda)(phen)4(H2O)2](ppda)2(H2O)} (1), {[Co(ppda)- (dpyo)(H2O)3]·4(H2O)}n (2), and {[Co(ppda)(bpe)]·(0.5H2O)}n (3) [ppda = 1,4- phenylenediacrylate; phen = 1,10-phenanthroline; dpyo = 4,4′-dipyridyl N,N′-dioxide; bpe = 1,2-bis(4-pyridyl)ethane] have been synthesized and characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction studies, and low-temperature magnetic measurements. The structural determination reveals that complex 1 is a discrete dinuclear species, 2 is a 1D polymeric chain, while 3 is a three-fold interpenetrated α-polonium network. Hydrogen-bonding interact…

Single-Ion Magnetic Behavior in CoII-CoIII Mixed-Valence Dinuclear and Pseudodinuclear Complexes

Two CoII–CoIII mixed-valence complexes of molecularformulas [Co2(H2L)2(H2O)2][Co2(H2L)2(H2O)(m-phth)]·8(H2O) {1;H2L2–= 2-[(2-hydroxy-3-methoxybenzylidene)amino]-2-(hydroxymethyl)propane-1,3-diolato, m-phth = 1,3-benzene-dicarboxylate} and [Co4(H2L)4(H2O)2(ppda)]·2(dmf)·3.2(H2O) {2;ppda = 1,4-phenylenediacrylate; dmf = N,N-dimethyl-formamide} were synthesized and characterized by single-crys-tal X-ray diffraction and magnetic studies at low temperature.The structural determination reveals that 1 is composed of di-nuclear ion pairs, namely, a cationic [Co2(H2L)2(H2O)2]+(1+) andan anionic [Co2(H2L)2(H2O)(m-phth)]–(1–) unit. In each of these ions, the CoIIand CoIIIcenters present distorted octa…

A Functionalized Noncovalent Macrocyclic Multiporphyrin Assembly from a Dizinc(II) Bis-Porphyrin Receptor and a Free-Base Dipyridylporphyrin

The bis-porphyrin system ZnP 2 , in which two zinc porphyrins are connected by a phenanthroline linker in an oblique fashion, acts as a bifunctional receptor towards the complexation of free-base meso-5,10-bis(4'-pyridyl)-15,20-diphenylporphyrin (4'-cisDPyP). In solution, NMR spectroscopy evidenced quantitative formation of the tris-porphyrin macrocyclic assembly ZnP 2 (4'-cisDPyP), in which the two fragments are held together by two axial 4'-N(pyridyl)-Zn interactions. The remarkable stability of the edifice (an association constant of about 6 x 10 8 M - 1 was determined by UV/Vis absorption and emission titration experiments in toluene) is due to the almost perfect geometrical match betwe…

A novel class of interpenetrated 3-D network of a dimeric cupric-tetracarboxylate unit

The hydrothermal reaction of Cu(II), fumaric acid and 4,4′-bipyridine (bpy) in equimolar amounts at 160 °C resulted in a new type of two-fold interpenetrating 3-D coordination network composed of tetracarboxylate dicopper(II) units bridged by bipyridine spacers.

Hexanuclear copper(ii) cage with {Cu3O⋯H⋯OCu3} core supported by a dicompartmental oxime ligand with m-xylyl spacer: synthesis, molecular structure and magnetic studies

A new dicompartmental dioxime ligand (H(2)L) with m-xylyl spacer between the donor sites has been synthesised by Schiff-base condensation of α,α'-diamino-m-xylene and diacetyl monooxime. The ligand reacts with copper(ii) salts giving rise to hexanuclear tricationic copper(II) cage complexes [Cu(II)(6)(μ(3)-O···H···O-μ(3))L(3)(H(2)O)(6)]X(3) (X = BF(4), 1a; X = ClO(4), 1b). The complexes have been characterised by different analytical and spectroscopic techniques and confirmed the hexanuclear structure even in solution. Single crystal X-ray diffraction studies of both the complexes revealed a very similar core structure with three dicompartmental ligands supporting two triangular Cu(3)O core…

Novel mixed-valence Cu compounds formed by Cu(II) dimers with double oximato bridges: in situ formation of anionic layer [Cu2(SCN)3]n(n-).

Two new N3O donor ketoxime Schiff bases (HL(1) and HL(2)) have been synthesized by condensing N,N-dimethylethylenediamine with diacetylmonoxime and benzilmonoxime, respectively in a 1:1 ratio. Reaction of Cu(ClO4)2·6H2O with HL(1) resulted in a discrete oximato-bridged dinuclear Cu(II) complex [Cu2(L(1))2(H2O)2](ClO4)2 (1). The same reaction in presence of NaSCN affords the complex {[Cu(II)2(L(1))2][Cu(I)4(μ(1,3)-SCN)4(μ(1,1,3)-SCN)2]}n (2), where partial Cu(II)→Cu(I) reduction is observed. In 2, arrays of [Cu(II)2(L(1))2](2+) cationic units are inserted in between 2D {[Cu(I)4(SCN)6](2-)}n layers and connected via μ(1,1,3)-SCN(-) links, thus forming a 3D network. On the other hand, reaction…

Bis[S-hexyl 3-(thiophen-2-ylmethylidene)dithiocarbazato-κ2N3,S]palladium(II)

In the title complex, [Pd(C12H17N2S3)2], the PdIIatom exhibits a square-planar coordination geometry with theN,S-chelating ligands arranged in atransconfiguration. Intramolecular C—H...S hydrogen bonds are observed. In the crystal, molecules are linked by weak C—H...N hydrogen-bond interactions, forming chains parallel to thebaxis.

A Three-Dimensional Homometallic Molecular Ferrimagnet

Isolation of Four New CoII/CoIII and NiII Complexes with a Pentadentate Schiff Base Ligand: Syntheses, Structural Descriptions and Magnetic Studies

In this paper we report the temperature and pH dependent syntheses and systematic characterization of four new Co(II)/Co(III) and Ni(II) complexes with a pentadentate Schiff base ligand H(3)L obtained by condensing 1,3,-diaminopropan-2-ol with 2-hydroxyacetophenone in 1:2 molar ratio. The room temperature syntheses involving Co(II) and Ni(II) nitrates and the ligand H(3)L lead to the isolation of the dinuclear species [Co(2)L(2)(H(2)O)] (1), and the mononuclear complex [Ni(LH)] (3), respectively, whereas refluxing at basic pH leads to the tetranuclear complexes, [Co(II)(2)Co(III)(2)L(2)(μ(3)-OMe)(2)(NO(3))(H(2)O)(2)]NO(3)·2(H(2)O) (2), and [Ni(4)L(2)(μ(3)-OMe)(2)(H(2)O)(2)]·2H(2)O (4). 1 is…

124I Radiolabeling of a AuIII‐NHC Complex for In Vivo Biodistribution Studies†

Abstract AuIII complexes with N‐heterocyclic carbene (NHC) ligands have shown remarkable potential as anticancer agents, yet their fate in vivo has not been thoroughly examined and understood. Reported herein is the synthesis of new AuIII‐NHC complexes by direct oxidation with radioactive [124I]I2 as a valuable strategy to monitor the in vivo biodistribution of this class of compounds using positron emission tomography (PET). While in vitro analyses provide direct evidence for the importance of AuIII‐to‐AuI reduction to achieve full anticancer activity, in vivo studies reveal that a fraction of the AuIII‐NHC prodrug is not immediately reduced after administration but able to reach the major…

Crystal structure ofS-octyl (E)-3-(4-methoxybenzylidene)dithiocarbazate

As already observed in similar molecules, the dithiocarbazate group in the title compound, C17H26N2OS2, adopts anEEconfiguration with respect to the C=N bond of the benzylidene moiety. In the crystal, molecules are connected into inversion dimers by pairs of N—H...S hydrogen bonds. The dimers are linked by weak π–π interactions, with centroid-to-centroid distances of 3.723 (11) Å, forming chains parallel to [110].

The first metamagnetic one-dimensional molecular material with nickel(ii) and end-to-end azido bridges

A novel single azido bridged one-dimensional Ni(II) chain, which represents the first metamagnetic one-dimensional metal–azido system with only end-to-end azido bridges, has been synthesised and characterised by a low temperature magnetic study. Lloret Pastor, Francisco, Francisco.Lloret@uv.es

The key role of hydrogen bonding in the nuclearity of three copper(II) complexes with hydrazone-derived ligands and nitrogen donor heterocycles

International audience; Three new Cu(II) complexes of formula [Cu(L1)(pyz)(CH3OH)]ClO4 (1), [Cu(L1)(4,4′-bpy)(ClO4)]·0.5H2O (2) and [{Cu(L2)(ClO4)}2(μ-4,4′-bpy)] (3) have been synthesised by using pyrazine (pyz) and 4,4′-bipyridine (4,4′-bpy) and tridentate O,N,O-donor hydrazone ligands, L1H and L2H, obtained by the condensation of 1,1,1-trifluoro-2,4-pentanedione with salicyloylhydrazide and benzhydrazide, respectively. The ligands and their complexes have been characterized by elemental analyses, FT-IR, and UV–Vis spectroscopies. Single crystal X-ray structure analysis evidences the metal ion in a slightly deformed square pyramidal geometry in all the complexes. However complexes 1 and 2 …

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