Solvatomorphism in a series of copper(II) complexes with the 5-phenylimidazole/perchlorate system as ligands.

In the course of an investigation of the supramolecular behaviour of copper(II) complexes with the 5-phenylimidazole/perchlorate ligand system (`blend') remarkable solvatomorphism has been observed. By employing a variety of crystallization solvents (polar protic, polar/non-polar aprotic), a series of 12 crystalline solvatomorphs with the general formula [Cu(ClO)(LH)]·x(solvent) have been obtained [LH = 5-phenylimidazole, x(solvent) = 3.3(HO) (1), 2(methanol) (2), 2(ethanol) (3), 2(1-propanol) (4), 2(2-propanol) (5), 2(2-butanol) (6), 2(dimethylformamide) (7), 2(acetone) (8), 2(tetrahydrofurane) (9), 2(1,4-dioxane) (10), 2(ethyl acetate) (11) and 1(diethyl ether) (12)].

Heterometallic clusters based on an uncommon asymmetric "V-shaped" [Fe(μ-OR)Ln(μ-OR)Fe] (Ln = Gd, Tb, Dy, Ho) structural core and the investigation of the slow relaxation of the magnetization behaviour of the [FeDy] analogue.

The synthesis, crystal structures, Mössbauer spectra and variable temperature dc and ac magnetic susceptibility studies of a new family of trinuclear heterometallic Fe/Ln complexes, [FeLn(PhCO)((py)CO)((py)C(OMe)O)(NO)Cl] (Ln = Gd (1/Gd), Tb (1/Tb), Dy (1/Dy), and Ho (1/Ho)), where (py)CO and (py)C(OMe)O are the anions of the -diol and hemiketal derivatives of di-2-pyridyl ketone, are reported. Compounds 1/Ln are based on an asymmetric "V-shaped" [Fe(μ-OR)Ln(μ-OR)Fe] structural core formed from the connection of the two terminal Fe centers to the central Ln ion either through one or two alkoxide groups originating from the alkoxide-type bridging ligands. Direct current magnetic susceptibility studies reveal the presence of weak antiferromagnetic interactions between the Fe ions.

New Apoptosis Inducers Containing Anti-inflammatory Drugs and Pnictogen Derivatives: A New Strategy in the Development of Mitochondrial Targeting Chemotherapeutics.

{[Ag(Mef)(μ--DMSO)(μ--DMSO)(-DMSO)]·2(HO)} (), [Ag(Mef)(tpP)] (), [Ag(Mef)(tpAs)] (), and {2 [Ag(Mef)(tpSb)] (DMSO)} () were obtained by the conjugation of mefenamic acid (MefH), a nonsteroidal anti-inflammatory drug (NSAID), with a mitochondriotropic derivative of pnictogen tpE (tp = triphenyl group; E = P, As, and Sb) through silver(I). Their hydrophilicity was adjusted by their dispersion into sodium lauryl sulfate (SLS), forming SLS@-. - and SLS@- were characterized by their spectral data and X-ray crystallography.

Synthesis and Biomedical Applications of Highly Porous Metal-Organic Frameworks.

In this review, aspects of the synthesis, framework topologies, and biomedical applications of highly porous metal-organic frameworks are discussed. The term "highly porous metal-organic frameworks" (HPMOFs) is used to denote MOFs with a surface area larger than 4000 m g. Such compounds are suitable for the encapsulation of a variety of large guest molecules, ranging from organic dyes to drugs and proteins, and hence they can address major contemporary challenges in the environmental and biomedical field.

Novel Co and Ni Metal Complexes and Ferromagnets by the Combination of 2-Pyridyl Oximes with Polycarboxylic Ligands.

The use of 2-pyridyl oximes in metal complexes chemistry has been extensively investigated in the last few decades as a fruitful source of species with interesting magnetic properties. In this work, the initial combination of pyridine-2-amidoxime (pyaoxH) and 2-methyl pyridyl ketoxime (mpkoH) with isonicotinic acid (HINA) and 3,5-pyrazole dicarboxylic acid (Hpdc) has provided access to three new compounds, [Ni(INA)(pyaox)(pyaoxH)(DMF)] (), [Co(mpko)(mpkoH)(OMe)(HO)](ClO) (), and [Co(OH)(Hpdc)(Hpdc)] (). displays a square-planar metal topology, being the first example that bears simultaneously HINA and pyaoxH in their neutral or ionic form.

NUIG4: A biocompatible pcu metal-organic framework with an exceptional doxorubicin encapsulation capacity.

Metal-organic frameworks (MOFs) are promising multifunctional porous materials for biomedical and environmental applications. Here, we report synthesis and characterization of a new MOF based on the tetrahedral secondary building unit [ZnO(CBAB)] (NUIG4), where CBABH = 4-((4-carboxybenzylidene)amino)benzoic acid. NUIG4 belongs to the family of MOFs with primitive cubic pcu topology, being a rare example with 4-fold interpenetration.

High nuclearity structurally - related Mn supertetrahedral T4 aggregates.

The simultaneous employment of 1,3-propanediol and di-2-pyridyl ketone in Mn carboxylate chemistry has provided access to three new, structurally-related [Mn] and [Mn] clusters. They are based on nanosized supertetrahedal T4 Mn/O structural cores and exhibit slow relaxation of magnetization below 3.5 K.

Expanding the NUIG MOF family: synthesis and characterization of new MOFs for selective CO adsorption, metal ion removal from aqueous systems, and drug delivery applications.

Metal organic frameworks (MOFs) have attracted considerable attention in recent years due to their use in a wide range of environmental, industrial and biomedical applications. The employment of benzophenone-4,4'-dicarboxylic acid (bphdcH2) in MOF chemistry provided access to the 3D mixed metal MOFs [CoNa2(bphdc)2(DMF)2]n (NUIG2) and [ZnK2(bphdc)2(DMF)2]n (NUIG3), and the 2D homometallic MOF [Co2(OH)(bphdcH)2(DMF)2(H2O)2]n(OH)·DMF (1·DMF). 1·DMF is based on a dinuclear SBU and consists of interpenetrating networks with an sql topology.

From 1D Coordination Polymers to Metal Organic Frameworks by the Use of 2-Pyridyl Oximes.

The synthesis and characterization of coordination polymers and metal-organic frameworks (MOFs) has attracted a significant interest over the last decades due to their fascinating physical properties, as well as their use in a wide range of technological, environmental, and biomedical applications. The initial use of 2-pyridyl oximic ligands such as pyridine-2 amidoxime (Hpyaox) and 2-methyl pyridyl ketoxime (Hmpko) in combination with 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid), Hpma, provided access to nine new compounds whose structures and properties are discussed in detail. Among them, [Zn(pma)(Hpyaox)(HO)] () and [Cu(OH)(pma)(mpko)] () are the first MOFs based on a 2-pyridyl oxime with possessing a novel 3,4,5,8-c net topology.

Influence of ligand positional isomerism on the molecular and supramolecular structures of cobalt(II)-phenylimidazole complexes.

In a study to evaluate the impact of flexible positional isomeric ligands on the coordination geometry and self-assembly process of 3d metal complexes, the synthesis of eight new cobalt(II) complexes with the 2-phenylimidazole (LH) and 5-phenylimidazole (L'H) ligands has been carried out. A variety of parameters/conditions have been probed using the general Co/X/LH or L'H (X = Cl, Br, I, NO, NCS, ClO, SO) reaction system. Interestingly, X-ray analyses reveal two distinct groups of complexes: reactions with LH only lead to tetrahedral or quasi-tetrahedral complexes {i.

Giant Heterometallic [MnNi] and [MnCo] "Loops-of-Loops-and-Supertetrahedra" Molecular Aggregates.

We report the synthesis, crystal structures and magnetic properties of the giant heterometallic [MnNi] (compounds , )/[MnCo] (compound ) "loops-of-loops-and-supertetrahedra" molecular aggregates and of a [MnNi] compound (cation of ) that is structurally related with the cation co-crystallizing with the anion of . In particular, after the initial preparation and characterization of compound [MnNi(μ-O)(μ-OH)(μ-Cl)(OCCH)(py)][MnNi(μ-O)(μ-O)(μ-Cl)Cl(OCCH)(pd)(py)] () we targeted the isolation of (i) both the cationic and the anionic aggregates of in a discrete form and (ii) the Mn/Co analog of [MnNi] aggregate. Our synthetic efforts toward these directions afforded the discrete [MnNi] "loops-of-loops-and-supertetrahedra" aggregate [MnNi(μ-O)(μ-O)(μ-Cl)Cl(OCCH)(pd)(py)(HO)] (), the heterometallic Mn/Co analog [MnCo(μ-O)(μ-O)(μ-Cl)Cl(μ-OCHCH)(OCCH)(pd)(py)] () and the discrete [MnNi] cation [MnNi(μ-O)(μ-OH)(μ-Cl)(OCCH)(py)](ClO)(OH) ().

Poly Organotin Acetates against DNA with Possible Implementation on Human Breast Cancer.

Two known tin-based polymers of formula {[R₃Sn(CH₃COO)]} where R = -Bu⁻ () and R = Ph⁻ (),were evaluated for their in vitro biological properties. The compounds were characterized via their physical properties and FT-IR, Sn Mössbauer, and ¹H NMR spectroscopic data. The molecular structures were confirmed by single-crystal X-Ray diffraction crystallography.

New metalo-therapeutics of NSAIDs against human breast cancer cells.

The non steroidal anti-inflammatory drugs (NSAID's)-silver(I) metallodrugs of aspirin (aspH), salicylic acid (salH), naproxen (napH) acid or p-hydrobenzoic acid (pHbzaH) and the mitochondriotropic triphenylarsine (tpAs) with the formulae [Ag(asp)(tpAs)] (1), [Ag(salH)(tpAs)] (2), [Ag(nap)(tpAs)] (3) and {[Ag(pHbza)(tpAs)]∙(dmf)} (4) and [Ag(tpAs)(NO)] (5) have been synthesized and characterized by m.p., FT-IR, UV-vis and H NMR, spectroscopic techniques and X-ray crystallography.

Heterometallic MnLn (Ln = Dy, Gd, Tb) Cross-Shaped Clusters and Their Homometallic MnMn Analogues.

The employment of di-2-pyridyl ketone, (py)CO, in heterometallic Mn/4f and homometallic Mn cluster chemistry has yielded six MnLn and two MnMn structurally related clusters, namely, [MnLnO{(py)CO}(NO)(RCO)(HO)](NO) (Ln = Gd, 1, 5; Dy, 2; Tb, 3; R = Et, 1-3; Me, 5), [MnDyO{(py)CO}(NO)(EtCO)(HO)(MeOH)]·0.7MeOH·0.8HO (4·0.

Binding of ligands containing carbonyl and phenol groups to iron(iii): new Fe, Fe and Fe coordination clusters.

The initial use of ligands 2'-hydroxyacetophenone (HL), 2-hydroxybenzophenone (HL) and 2,2'-dihydroxybenzophenone (HL) in iron(iii) chemistry is described. The syntheses and crystal structures are reported for five iron(iii) clusters: [FeO(OMe)(L)(MeOH)](NO)·3MeOH (1·3MeOH), [FeO(OH)(OMe)(L)](ClO)·2HO (2·2HO), [FeO(OMe)Cl(L)(MeOH)] (3), [FeO(OMe)(L)(py)](ClO)·MeOH (4·MeOH), where py = pyridine, and [FeO(OEt)(OCMe)(L)(HL)] (5). The molecular structures of the decanuclear clusters 1, 3 and 4 are organized around a {Fe(μ-O)(μ-OMe)(μ-OMe)} core consisting of ten {FeO} face-sharing defective cubane units.

In search of molecules displaying ferromagnetic exchange: multiple-decker Ni and Ni complexes from the use of pyridine-2-amidoxime.

The use of pyridine-2-amidoxime (pyaoxH) in Ni chemistry has provided access to a dodecanuclear complex and a hexadecanuclear Ni cluster, namely [Ni(pyaox)(pyaoxH)(MeOH)Cl]Cl·5MeOH (1·5MeOH) and [Ni(pyaox)(pyaoxH)(MeOH)](SO)·10HO·26MeOH (2·10HO·26MeOH). Complex 1·5MeOH was isolated by the reaction of NiCl·6HO, pyaoxH and NaOMe in a 1 : 1 : 2 molar ratio in MeOH in 60% yield. Treatment of NiSO·6HO with pyaoxH and NEt in a 1 : 1 : 2 molar ratio in MeOH afforded 2·10HO·26MeOH in good yield (65%).

Nimesulide Silver Metallodrugs, Containing the Mitochondriotropic, Triaryl Derivatives of Pnictogen; Anticancer Activity against Human Breast Cancer Cells.

Novel silver(I) metallo-drugs of the nonsteroidal anti-inflammatory drug nimesulide (nim) and the mitochondriotropic triaryl derivatives of pnictogen ligands (tpE, E = P (tpp, tptp, or totp), As (tpAs), Sb (tpSb)) with the formulas {[Ag(nim) (tpp)2]DMF} (1), [Ag(nim) (tptp)2] (2), [Ag(nim) (totp)] (3), [Ag(nim) (tpAs)2] (4), and [Ag(nim) (tpSb)3] (5) ((tpp = triphenyphosphine, tptp = tri(p-tolyl)phosphine, totp = tri(o-tolyl)phosphine, tpAs = triphenylarsine, tpSb = triphenylantimony, and DMF = dimethylformamide) were synthesized and characterized by melting point, vibrational spectroscopy (mid-Fourier transform IR), (1)H NMR, UV-visible spectroscopic techniques, and X-ray crystallography. The in vitro cytotoxic activity of 1-5 against human breast adenocarcinoma cancer cell lines: MCF-7 (estrogen receptor (ER) positive) and MDA-MB-231 (ER negative) was determined. The genotoxicity on normal human fetal lung fibroblast cells (MRC-5) caused by 1-5 was evaluated by fluorescence microscopy.

Introducing Dimensionality to the Archetypical Mn12 Single-Molecule Magnet: a Family of [Mn12]n Chains.

The [Mn12O12(O2CR)16(L4)] family (R = various; L = terminal ligand) of clusters holds a special place in molecular magnetism; they are the most well-studied single-molecule magnets (SMMs). Targeted linkage of these SMMs has now been achieved for the first time. The resulting chain structures have been confirmed crystallographically, and the magnetic properties, up to 1.

Filling the gap between the quantum and classical worlds of nanoscale magnetism: giant molecular aggregates based on paramagnetic 3d metal ions.

In this review, aspects of the syntheses, structures and magnetic properties of giant 3d and 3d/4f paramagnetic metal clusters in moderate oxidation states are discussed. The term "giant clusters" is used herein to denote metal clusters with nuclearity of 30 or greater. Many synthetic strategies towards such species have been developed and are discussed in this paper.

Experimental and Theoretical Insight into Electrocatalytic Hydrogen Evolution with Nickel Bis(aryldithiolene) Complexes as Catalysts.

A series of neutral and monoanionic nickel dithiolene complexes with p-methoxyphenyl-substituted 1,2-dithiolene ligands have been prepared and characterized with physicochemical methods. Two of the complexes, the monoanion of the symmetric [Ni{S2C2(Ph-p-OCH3)2}2] (3(-)) with NBu4(+) as a counterion and the neutral asymmetric [Ni{S2C2(Ph)(Ph-p-OCH3)}2] (2), have been structurally characterized by single-crystal X-ray crystallography. All complexes have been employed as proton-reducing catalysts in N,N-dimethylformamide with trifluoroacetic acid as the proton source.

A single-chain magnet based on linear [Mn(III)2Mn(II)] units.

The synthesis, structural characterization and magnetic properties of a 1D coordination polymer based on a linear mixed valent [Mn(III)2Mn(II)] repeating unit are described. It displays single-chain magnet (SCM) behaviour with an energy barrier of ∼38 K and represents the first example of a mixed valent Mn-carboxylate SCM with a linear architecture.

Discrete and encapsulated molecular grids: homometallic Mn15 and heterometallic Mn24Ni2 aggregates.

Two molecular grid-like clusters are reported, one is a discrete [3 × 5] grid and the other a [3 × 4] grid within a Mn12Ni2 loop. Both Mn24Ni2 and Mn15 aggregates display novel and aesthetically pleasing structures with the former one being among the highest nuclearity heterometallic MnxMy clusters (M = any transition metal ion).

A MnII6MnIII6 single-strand molecular wheel with a reuleaux triangular topology: synthesis, structure, magnetism, and DFT studies.

The use of the anion of 3-methyl-1,3,5-pentanetriol (mpt(3-)) in manganese carboxylate chemistry has afforded the new Mn(II/III)12 cluster [Mn(II)6Mn(III)6(mpt)6(CH3CO2)12(py)6]·3CH3CN (1·3CH3CN). Complex 1 was isolated in moderate yield by the reaction of Mn(CH3CO2)2·4H2O and H3mpt in a 2.6:1 molar ratio in a solvent mixture of acetonitrile and pyridine.