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The metalloantibiotic of formula Ph2Sn(CIP)2 (CIPTIN) (HCIP = ciprofloxacin) was synthesized by reacting ciprofloxacin hydrochloride (HCIP·HCl) (an antibiotic in clinical use) with diphenyltin dichloride (Ph2SnCl2DPTD). The complex was characterized in the solid state by melting point, FT-IR, X-ray Powder Diffraction (XRPD) analysis, 119Sn Mossbauer spectroscopy, X-ray Fluorescence (XRF) spectroscopy, and Thermogravimetry/Differential Thermal Analysis (TG-DTA) and in solution by UV-Vis, 1H NMR spectroscopic techniques and Electrospray Ionisation Mass Spectrometry (ESI-MS). The crystal structure of CIPTIN and its processor HCIP was also determined by X-ray crystallography. The antibacterial activity of CIPTIN, HCIP·HCl, HCIP and DPTD was evaluated against the bacterial species Pseudomonas aeruginosa (P. aeruginosa), Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Staphylococcus epidermidis (S. epidermidis), by the means of Minimum Inhibitory Concentration (MIC), Minimum Bactericidal Concentration (MBC) and Inhibition Zones (IZs). CIPTIN shows lower MIC values than those of HCIP·HCl (up to 4.2-fold), HCIP (up to 2.7-fold) or DPTD (>135-fold), towards the tested microbes. CIPTIN is classified into bactericidal agents according to MBC/MIC values. The developing IZs are 40.8 ± 1.5, 34.0 ± 0.8, 36.0 ± 1.1 and 42.7 ± 0.8 mm, respectively which classify the microbes P. aeruginosa, E. coli, S. aureus and S. epidermidis to susceptible ones to CIPTIN. These IZs are greater than the corresponding ones of HCIP·HCl by 1.1 to 1.5-fold against both the tested Gram negative and Gram positive bacteria. CIPTIN eradicates the biofilm of P. aeruginosa and S. aureus more efficiently than HCIP·HCl and HCIP. The in vitro toxicity and genotoxicity of CIPTIN were tested against human skin keratinocyte cells (HaCaT) (IC50 = 2.33 μM). CIPTIN exhibits 2 to 9-fold lower MIC values than its IC50 against HaCaT, while its genotoxic effect determined by micronucleus assay is equivalent to the corresponding ones of HCIP·HCl or HCIP.

Two new heterometallic clusters exhibiting related cores, [Mn9Ni2(μ3-Ο)10(μ3-Cl)2(O2CMe)11 (py)4(H2O)4]∙2H2O (1∙2H2O) (py = pyridine) and [Mn9Co2(μ3-Ο)10(μ3-ΟΗ)2(O2CEt)10(EtOH)3(H2O)(py)5](ClO4)2Cl (2) are reported. Compounds 1∙2H2O / 2 were prepared from reactions of [Mn3O(O2CMe)6(py)3]∙py / [Mn3O(O2CEt)6(py)3](ClO4) with MCl2∙6H2O (M = Ni2+, Co2+) and (Bun4N)MnO4 in a 1:3:0.1 / 1:1:0.1 molar ratio in MeCN (15 ml) / MeOH-EtOH (15-0.5 ml) in ∼ 28 % /

A series of new compounds prepared from reactions of pyridine-3,5-dicarboxylic acid (PDCH2), bipositive d-metal ions (Cd2+, Zn2+, Co2+ and Cu2+) and various template molecules [1,3-propanediol (pdH(2)), diethanolamine (deaH(3)), N-phenyldiethanolamine (phdeaH(2)), triethanolamine (teoaH(3)), 2-hydroxymethylpyridine (2hmpH), 3-hydroxymethylpyridine (3hmpH), 3-hydroxypropylpyridine (3hppH), and 4-hydroxymethylpyridine (4hmpH)] are reported. Among them, [[(CH3)(2)NH2](2)[Cd-2(PDC)(3)]](n).4nDMF.6nH(2)O, [1], [Mn(PDC)(DMF)](n), [2], [Mn-3(PDC)(2)(INA)(2)(DMF)(1.5)(H2O)(0.5)](n).nDMF.2nH(2)O, [3], and [Zn(PDC)(NMP)](n).nH(2)O, [4], are 3D coordination polymers, [Zn(PDC)(H2O)(DMF)](n), [5], [Zn(PDC)(3hmpH)](n.)nDMF.0.5nH(2)O, [6], and [Co(PDC)(3hmpH)(2)](n).0.25nDMF, [8], have 2D polymeric structures, while [Zn(PDC)(2hmpH)(2)](2).2DMF, [7], is a 0D binuclear complex, and [Cu(PDC)(3hmpH)(2)](n).0.5nDMF1.5nH(2)O, [9], is a chain polymer. Topological analysis reveals that some of the compounds display unusual structural architectures and two of them, in particular [1] and [3], present new topological types. The effect of the use of amino alcohol/polyol templates on the formation of the new compounds is also discussed in detail. The thermal stability of the prepared complexes was also studied. This study represents the initial systematic investigation on the use of a combination of polytopic nitrogen and oxygen-donor ligands and amino- or pyridine-alcohol templates for the synthesis of new MOFs.

The synthesis and characterization of {[Co5(INA)3(HCOO)7(DMF)(H2O)]·2DMF·4H2O}∞ (INA– = the anion of isonicotinic acid) denoted as Co5‐INA·2DMF·4H2O is reported. The compound was isolated from the reaction of Co(NO3)2·6H2O with HINA in the presence of HCOOH in N,N‐dimethylformamide (DMF) at 100 °C. It exhibits a rigid 3‐D porous structure based on Co5 repeating units which are linked through carboxylate ligands (from HCOO– and INA–) to form an infinite rod‐shaped secondary building unit (SBU). The rods are connected through isonicotinate ligands to produce a unique (3,3,4,4,4‐coordinated) 5‐nodal 3D network with point symbol (4.5.6.72.9)(4.5.62.7.8)(4.5.7)2(5.62.73). Gas sorption studies revealed that Co5‐INA displays a microporous structure with BET area 264.5 m2 g–1 and CO2 uptake of 1.96/1.29 mmol·g–1 at 273/298 K (1 bar), respectively. Magnetism studies revealed that Co5‐INA displays spin canting behavior with a spin glass relaxation process at ca. 5.0 K.

An efficient route for the synthesis of two amphiphilic type I [3:3]-hexakis adducts of C60 equipped with enantiopure cyclo-monomalonate addends was explored. Studies on their self-assembling behavior by TEM and SEM revealed that minor modification of the size and chemical nature of their glycol-substituted monomalonate addends and, consequently, of the shape of these giant molecules significantly influences their corresponding self-assembling architectures.

The pyridine-2,6-dicarboxylic acid or dipicolinic acid (H2DPA) is a unique biomarker for the detection of bacterial spores. Therefore the qualitative and quantitative determination of H2DPA is crucial for the timely detection of bacteria. Here, the first analysis of H2DPA which is based on the fluorescence of coinage metal complexes is reported. Catechol oxidase, on the other hand, is a copper containing oxidase enzyme that catalyzes the oxidation of ortho-diphenols into ortho-quinones. The catechol oxidation reaction is used in the determination of catecholamines, adrenaline, noradrenaline, dopamine, etc. Therefore, the development of new copper complexes which act as catechol oxidase models can be applied in the detection of these hormonally (adrenaline, noradrenaline, dopamine, etc.) active compounds. Thus, the copper(I) complex of dipicolinic acid (H2DPA) with formulae [CuI(ΗDPA)(ΤPP)2] ·H2O (1) (TPP = triphenylphosphine) and the mixed valence copper(I/II) one with formulae {[CuII(DPA)(H2DPA)] · [CuI(TPP)3]2}·2DMSO (2) have been synthesized and characterized by m.p., FT-IR, UV–vis, Fluorescence and 1H NMR spectroscopic techniques and X-ray crystallography. These complexes (1–2) and the known ones [CuΙI(DPA)(H2DPA)] (3) and [Cu2Cl2(TPP)3] (4) were used for the evaluation of their fluorescence properties. The excitation wavelengths maxima are observed at 350 nm while they emit at 407–496 nm. The catalytic activities of 1–3 on the oxidation of 3,5-di-tertbutyl-o-catechol to 3,5-di-tert-butyl-o-quinone were also studied spectrophotometrically. The high yields of 2 and 3 suggest their biomimetic behavior with catechol oxidase.

The reaction of a suspension of arsenic(III) oxide in deoxygenated methanol with redistilled 4-aminothiophenol at 25◦C for 24 h afforded tris(4-aminophenylthio)arsine. Crystals suitable for X-ray analysis were obtained by recrystallization from chloroform. The compound is monoclinic [P21/n, 11.6427(2) A, 9.3726(2) A, 17.7788(4) A, = 99.854(2)◦, Z = 4]. Its supramolecular organization is based on strong (N-H· · ·N, N-H· · ·S) and weak (C-H· · ·S) intermolecular hydrogen bonding together with C-H· · ·π interactions among the discrete molecular units. The crystal data of this and other As(III) trithiolates are compared and discussed in the light of probable operation of the -effect in their nucleophilic reactions.

The missing VIV11VV7 oxidation-state member of the polyoxooctadecavanadate(IV/V) — azide family of inorganic host-guest systems has been incorporated in a NaI-containing 3D architecture; the complex shows remarkable inhibition properties on human platelet aggregation and antitumoural activity against cancer cell lines.

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. Attempts are made to categorize some of the most successful methods to giant clusters, but it will be pointed out that the characteristics of the crystal structures of such compounds including nuclearity, shape, architecture, etc. are unpredictable depending on the specific structural features of the included organic ligands, reaction conditions and other factors. The majority of the described compounds in this review are of special interest not only for their fascinating nanosized structures but also because they sometimes display interesting magnetic phenomena, such as ferromagnetic exchange interactions, large ground state spin values, single-molecule magnetism behaviour or impressively large magnetocaloric effects. In addition, they often possess the properties of both the quantum and the classical world, and thus their systematic study offers the potential for the discovery of new physical phenomena, as well as a better understanding of the existing ones. The research field of giant clusters is under continuous evolution and their intriguing structural characteristics and magnetism properties that attract the interest of synthetic Inorganic Chemists promise a brilliant future for this class of compounds.

The preparation and crystal structure of a tetranuclear Ni(II) sulfato cluster containing the anion of di-2-pyridyl ketone oxime, (py)2CNO−, are reported. Treatment of NiSO4·6H2O with one equivalent of (py)2CNOH and one equivalent of NEt3 in MeOH leads to the compound [Ni4{(py)2CNO}4(SO4)2(MeOH)4] (1) in moderate yield. The metal ions are linked together by two 3.2111 and two 2.1110 (Harris notation) (py)2CNO− ligands, as well as two 2.1100 SO42− ions to create a rare metallacrown-type (12-MC-4) ring. Strong H-bond intermolecular interactions in 1 lead to the formation of a 1D chain along the axis. Characteristic IR bands are discussed in terms of the known structure of 1.

A new Cu2+ complex that was isolated from the initial use of 5-((pyridin-4-ylmethylene) amino) isophthalic acid (PEIPH2) in 3d metal-organic framework (MOF) chemistry is reported. Complex [Cu-3(PEIP)(2)(5-NH2-mBDC)(DMF)].7DMF8 denoted as Cu-PEIP.7DMF was isolated from the reaction of Cu(NO3)(2).2.5H(2)O with PEIPH2 in N, N-dimethylformamide (DMF) at 100 degrees C and contains both the PEIP2-ligand and its 5-NH2-mBDC(2)-fragment. After the structure and properties of Cu-PEIP were known an analogous complex was prepared by a rational synthetic method that involved the reaction of Cu(NO3)(2).2.5H(2)O, 5-((pyridin-4-ylmethyl) amino) isophthalic acid (PIPH2 - the reduced analogue of PEIPH2) and 5-NH2-mBDCH(2) in DMF at 100 degrees C. Cu-PEIP comprises two paddle-wheel [Cu-2(COO)(4)] units and exhibits a 3D-framework with a unique trinodal underlying network and point symbol (4.52)(4)(4(2).5(4).6(4).8(3).9(2))(2)(5(2).8(4)). This network consists of pillared kgm-a layers containing a hexagonal shaped cavity with a relatively large diameter of similar to 8-9 angstrom surrounded by six trigonal shaped ones with a smaller diameter of similar to 4-5 angstrom and thus resembles the structure of HKUST-1. Gas sorption studies revealed that Cu-PEIP exhibits a 1785 m(2) g(-1) BET area as well as high CO2 sorption capacity (4.75 mmol g(-1) at 273 K) and CO2/CH4 selectivity (8.5 at zero coverage and 273 K).

The synthesis and characterization of [Co-9(INA)(18)(H2O)(6)]center dot 11DMF center dot 15H(2)O(8) (Co-9-INA center dot 11DMF center dot 15H(2)O) (INA(-) = the anion of isonicotinic acid) is reported. It exhibits a rigid 3D-porous structure with a Co-9 repeating unit consisting of four [Co-2(II)(mu-O2CR)(2)(mu-H2O)] subunits (two unique) linked through bridging INA(-) ligands to an isolated Co-II ion (half unique). The [Co-2(II)] dimers and the isolated Co-II ion have assembled to create a trinodal (6,7,8)-coordinated network with point symbol (3(2).4(11).5(6).6(2))(2)(3(2).4(18).5(4).6(4))(2)(3(4).4(4).5(4).6(3)). Gas sorption studies revealed that Co-9-INA exhibits 910 m(2) g(-1) BET area, 4.2 mmol g(-1) CO2 uptake at 273 K/1 bar, and 6.7 CO2/CH4 selectivity at zero coverage. Furthermore, Co-9-INA displays capability for exchange of the guest solvent molecules by various organic molecules in a single-crystal to single-crystal fashion. Direct and alternating current magnetic susceptibility studies revealed the existence of dominant antiferromagnetic interactions between the Co2+ ions that result in a paramagnetic ST = 3/2 spin ground state value. Overall, this work emphasizes the potential of relatively simple and inexpensive polytopic ligands, such as isonicotic acid, to stabilize microporous MOFs with significant CO2 sorption capacity.

The Bingel functionalization of C60 (II) with a structurally novel tether (I) equipped with three reactive malonate groups affords a C2v-symmetrical eedge,eface,trans-1 trisadduct (III) in a complete regioselective manner.

A series of new Zn2+-trimesate (btc(3-)) metal organic frameworks (MOFs) has been isolated in the presence of various amino-alcohols under solvothermal conditions. Thus, the reaction of ZnCl2 with trimesic acid (H(3)btc) and the amino alcohols triethanolamine (teoa), 2(hydroxymethyl)piperidine (hmpip), N-tert-butyldiethanolamine (tbdeoa), 1,4-bis(2-hydroxyethyl)piperazine (bhep), N-methyldiethanolamine (mdeoa), or 4-(2-hydroxyethyl)morpholine (hem) in a 1.6:1:5.6 molar ratio in DMF afforded compounds (teoaH)(2)[Zn(btc)(1.33)] (MOAAF-1) (MOAAF = metal organic amino-alcohol framework), (NH2Me2)(2)(hmpipH)[Zn-3(btc)(3)] (MOAAF-2), (NH2Me2)-(tbdmaH)(2)[Zn-3(btc)(3)] (MOAAF-3) (tbdma = N-tert-butyl-dimethylamine), (NH2Me2)(bhepH(2))[Zn-3(btc)(3)] (MOAAF-4), (NH2Me2) [Zn-4(btc)(3)(mdeoa)(2)] (MOAAF-5), and (NH2Me2)[Zn-4(btc)(3)(hem)(2)] (MOAAF-6), respectively. The compounds display 3D structures with relatively large cavities (4-10 angstrom) and high potential solvent-accessible areas (38-68% of the unit cell volumes). A number of novel structural features are revealed in the reported MOFs, such as unprecedented dinuclear [Zn-2(COO)(5)](-1) secondary building units (SBUs) and unique network topologies (e.g., in compounds MOAAF-2, MOAAF-3, MOAAF-5, and MOAAF-6). The amino-alcohols employed played a key role for the appearance of such novel structural features in MOAAF 1-6 since they were found to act as bases responsible for the deprotonation of H(3)btc, templates, and chelating ligands. Specifically, most of the compounds synthesized were shown to be templated by protonated amino alcohols that are involved in hydrogen bonding interactions with the frameworks, whereas in two cases (compounds MOAAF-5 and MOAAF-6) the amino alcohols acted as chelating ligands affecting significantly the underline topology of the MOFs. The thermal stability and photoluminescence properties of the MOFs are also discussed. This work represents the initial systematic investigation on the use of combination of amino alcohols and polycarboxylate ligands for the synthesis of new MOFs, demonstrating it as a powerful synthetic strategy for the isolation of novel MOFs.

Two new Mn(15) clusters consisting of a supertetrahedron which is incorporated in a loop are reported. The reactions of [Mn(O(2)CEt)(2)]·2H(2)O with the diols 1,3-propanediol (H(2)pd) or 2-methyl-1,3-propanediol (H(2)mpd) in the presence of KX (X = CN(-), Cl(-), Br(-), NO(3)(-), ClO(4)(-), OCN(-), SCN(-)) afforded compounds [Mn(15)K(mu(4)-O)(4)(O(2)CEt)(11)(pd)(12)(py)(2)] (1) and [Mn(15)K(mu(4)-O)(4)(O(2)CEt)(11)(mpd)(12)(py)(2)] (2). The structural core of 1 and 2 consists of a Mn(11) loop and a Mn(9)K supertetrahedron sharing a Mn(5) triangle. To the best of our knowledge, the structural motif of a supertetrahedron incorporated in a loop appears for the first time in metal cluster chemistry. Variable-temperature, solid-state direct current (dc) magnetic susceptibility studies in the 300-5 K range showed that the chi(M)T value increases with decreasing T suggesting the existence of predominant ferromagnetic exchange interactions and a relatively large ground state spin. This was confirmed by field-variable temperature magnetization measurements which were fitted using a matrix diagonalization method to give S approximately 23/2, g = 1.92(1) and D = -0.071(2) cm(-1). In addition, compound 1 displays frequency-dependent alternating current (ac) signals suggesting single-molecule magnetism (SMM) behaviour. This was proven by magnetization vs. dc field sweeps on single-crystals of 1·0.7py·1.3MeCN, which displayed sweep rate- and temperature-dependent hysteresis loops.

The title compound, C23H26O6S2 was synthesized by esterification of tricyclo[3.3.1.03,7]nonane-3,7-diol with p-toluenesulfonyl chloride. The molecule has symmetry 2 and is situated on site 4e. The C—C bond length between the quartenary C atoms is 1.598 (2) Å, which is considerably longer than other C—C bonds in the molecule. There are C—H...O interactions present in the structure. As a consequence, the packing of the molecule (viewed along [100]) appears as chains where the molecules run parallel, but each chain has the opposite direction to the neighboring ones.

The title compound, C18H24I2, has an adamantanoid structure with tetrahedral cages having four C atoms lying on the same plane [(I—)C—C—C—C(—I) torsion angle = 0°]. The plane is extended by the two I atoms, each having a deviation of 1.0 (6) Å [C—C—C—I torsion angle = 178.9 (4)°]. The central C—C bond connecting the two quaternary carbons seems enlarged [1.593 (9) Å] in comparison to the corresponding bond in [2]diadamantane [1.554 (3) Å]. This is attributed to the presence of the electronegative I atoms, which affect inductively the C atoms of the four-C-atom plane, making the central C—C bond weaker.

The title compound, C18H24, was the main product of thermolysis of noradamantene dimer (heptacyclo[9.3.1.12,6.14,8.19,13.01,9.02,8]octadecane). The crystal structure was determined to prove that the thermolysis product of noradamantene dimer is favored by stretch release due to ring opening of the four-membered ring. The bond length of the quaternary C atoms of the starting material was calculated as 1.6 Å, enlarged in comparison to other single bonds. After the rearrangement, the stretch release of the above carbons leads to an increase of the distance between them (2.824 Å) with respect to the crystallographic data.

The crystal structure of the title compound, C9H12O4S, was determined in order to investigate the effect of the eclipsed O atoms on the bond length of the vicinal quaternary C atoms. The two quaternary C atoms of the noradamantane skeleton and the two O atoms to which they are connected all located essentially in the same plane (maximum deviation = 0.01 Å), resulting in an eclipsed conformation of the C—O bonds. The C—C bond of the quaternary C atoms is 1.581 (3) Å, considerably longer than the other C—C bonds of the molecule due to the stretch of the cage structure.