Paula Brandão

Polyaza Cryptand Receptor Selective for Dihydrogen Phosphate

A hexaamine cage with pyridyl spacers was synthesized in good yield by a [2+3] Schiff-base condensation followed by sodium borohydride reduction. The protonation constants of the receptor as well as its association constants with Cl(-), NO(3)(-), AcO(-), ClO(4)(-), SO(4)(2-), H(2)PO(4)(-), and H(2)AsO(4)(-) were determined by potentiometry at 298.2 +/- 0.1 K in H(2)O/MeOH (50:50 v/v) and at ionic strength 0.10 +/- 0.01 M in KTsO. These studies revealed that although dihydrogen phosphate is less charged than sulfate, it is still appreciably bound by the receptor at low pH, suggesting that the pyridyl nitrogen is accepting hydrogen bonds from dihydrogen phosphate. It is also shown that dihydrogen phosphate is capable of effectively competing with sulfate for the receptor at higher pH, being selective for hydrogen phosphate at pH about 7.0. (31)P NMR experiments supported these findings. The fact that the receptor shows such a marked preference for hydrogen phosphate based mainly in its hydrogen bond accepting/donating ability in a highly competitive medium such as water/methanol mixed solvent is quite remarkable. Single-crystal X-ray diffraction determinations of anion associations between H(6)pyr(6+) receptor and nitrate, sulfate, and phosphate are consistent with the existence of [(H(6)pyr)(NO(3))(3)(H(2)O)(3)](3+), [(H(6)pyr)(SO(4))(2)(H(2)O)(4)](2+), and [(H(6)pyr)(HPO(4))(2)(H(2)PO(4))(H(2)O)(2)](+) cations. One nitrate anion is embedded into the H(6)pyr(6+) cage of the first supermolecule whereas in the second and third ones the anions are located in the periphery of the macrobicycle.

A Trinuclear Copper(II) Cryptate and Its μ3‐CO3 Cascade Complex: Thermodynamics, Structural and Magnetic Properties

The 2,4,6-triethylbenzene-capped hexaamine macrobicycle with pyridyl spacers (pyr) was able to coordinate three copper(II) ions within its cavity. Potentiometric studies performed at 298.2 K in MeOH/H(2)O (50:50 v/v) and at ionic strength 0.10 mol dm(-3) in KNO(3) revealed that trinuclear species predominate in solution from pH 5.0, the hydroxo complexes being the main species, which start forming at unusual very low pH values. The single-crystal X-ray determination of the trinuclear complex showed that the three copper centres have square-planar geometry, arranged in an almost equilateral triangle, and have carbonate bridging the three metal centres. The presence of carbonate resulted from fixation of atmospheric CO(2). The present study represents the first μ(3)-CO(3)-bridged trinuclear copper(II) complex located in the interior of a macrobicyclic cavity. The magnetic data of [Cu(3)(pyr)(μ(3)-CO(3))]·(ClO(4))(4) showed ferromagnetic intramolecular interactions [J=3.80 cm(-1), based on the Hamiltonian H=-J(S(1)S(2)+S(2)S(3)+S(1)S(3))] yielding a spin quartet, S=3/2, ground state. Density functional calculations on the experimental geometry of the trinuclear complex showed that the ferromagnetic nature of the magnetic coupling can be attributed to the syn-anti conformation of the carbonato bridge, and a magneto-structural correlation, based on the different conformations (syn-anti, syn-syn and anti-anti), is presented. The interesting properties observed, namely the lowering of the pK(a) of coordinated water molecules to unusual values and the good fit of the carbonate anion between the copper centres, derive from the special architecture of pyr.

Dicarboxylate Recognition by Two Macrobicyclic Receptors: Selectivity for Fumarate over Maleate

Two ditopic polyamine macrobicyclic compounds have been studied as receptors for the recognition of dicarboxylate anions of varying chain length in aqueous solution. One of the receptors consists of two tris(2-aminoethyl)amine-derived binding subunits separated by p-xylyl spacers, while the other is a heteroditopic compound, combining two different head units, a tren-derived and a 2,4,6-triethylbenzene-derived one, also separated by p-xylyl spacers. The acid-base behavior of the compounds as well as their binding ability with oxalate (oxa(2-)), malonate (mal(2-)), succinate (suc(2-)), glutarate (glu(2-)), maleate (male(2-)) and fumarate (fum(2-)) anions were studied by potentiometry at 298.2 K in aqueous solution and at ionic strength 0.10 M in KTsO. NMR studies were also performed to obtain structural information in solution on the supermolecules formed by association of the protonated macrobicycles with the dicarboxylate substrates. The results revealed that both compounds are able to form stable associations with the dianionic substrates in competitive aqueous solution, with unprecedented selectivity for fum(2-) over other dicarboxylate competitors, including its cis isomer male(2-). In addition it was found that although the selectivity pattern is unaffected by the introduction of the 2,4,6-triethylbenzene head unit, the affinity toward dicarboxylates is significantly reduced. Therefore, the comparison between the binding behavior of these two receptors showed the effect of the increased rigidity and lipophilicity of the receptor with the 2,4,6-triethylbenzene head unit in the binding properties and the selectivity pattern.

Entanglement and Bell's inequality violation above room temperature in metal carboxylates.

In the present work we show that a particular family of materials, the metal carboxylates, may have entangled states up to very high temperatures. From magnetic-susceptibility measurements, we have estimated the critical temperature below which entanglement exists in the copper carboxylate {Cu-2(O2CH)(4)}{Cu(O2CH)(2)(2-methylpyridine)(2)}, and we have found this to be above room temperature (T-e similar to 630 K). Furthermore, the results show that the system remains maximally entangled until close to similar to 100 K and the Bells inequality is violated up to nearly room temperature (similar to 290 K).

Cyclam derivatives containing three acetate pendant arms: synthesis, acid–base, metal complexation and structural studies

The ligands 1,4,8,11-tetraazacyclotetradecane-1,4,8-triacetic-11-methylphosphonic acid (H5te3a1p) and 1,4,8,11-tetraazacyclotetradecane-1,4,8-triacetic acid (H3te3a) were synthesized, the former one for the first time. The syntheses of these ligands were achieved from reactions on 1,4,8,11-tetraazacyclotetradecane-1,4,8-tris(carbamoylmethyl) hydroiodide (te3am x HI), and compounds (Hte3am)+, 1, and (H7te3a1p)2+, 4, were characterized by X-ray diffraction. Structures of two other compounds resulting from side-reactions, (H2te2lac)2+, 2, and (H4te2a2pOEt2)2+, 4, were also determined by X-ray diffraction. Potentiometric titrations of H5te3a1p and H3te3a were performed at 298.2 K and ionic strength 0.10 mol dm(-3) in NMe4NO3 to determine their protonation constants. 1H and 31P NMR titrations of H5te3a1p were carried out in order to determine the very high first protonation constant of this ligand and to elucidate the sequence of protonation. Potentiometric studies of the two ligands with Ca2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ metal ions performed in the same experimental conditions showed that the complexes of H5te3a1p present very high thermodynamic stability while complexes of H3te3a, particularly Co2+ and Zn2+, are even more stable. 31P NMR spectra of the cadmium(II) complex of H5te3a1p showed that the phosphonate moiety was coordinated to the metal ion. The UV-vis-NIR spectroscopic data and magnetic moment values of Co2+ and Ni2+ complexes of H5te3a1p and H3te3a together with the EPR of the corresponding Cu2+ complexes indicated that all these complexes adopt distorted octahedral coordination geometries in solution. This was confirmed by the single crystal structure of [Cu2(Hte3a)(H2O)3Cl]Cl0.5(ClO4)0.5 x 2H2O that showed two distorted octahedral copper centres bridged by a N-acetate pendant arm with a CuCu distance of 4.890(1) A. The first one is encapsulated into the macrocyclic cavity surrounded by four nitrogen and two oxygen donors from the macrocycle, whereas the second one is on the periphery of the macrocycle and is coordinated to two oxygen atoms of one acetate pendant arm in chelating fashion, one chloride and three water molecules.

Facile synthesis, structural evaluation, antimicrobial activity and synergistic effects of novel imidazo[1,2-a]pyridine based organoselenium compounds.

A simple and efficient method has been described to synthesize the hitherto unknown imidazo[1,2-a]pyridine selenides (5a-l) by reaction of 2-chloroimidazo [1,2-a]pyridines with aryl/heteroaryl selenols, generated in situ by reduction of various diselenides with hypophosphorous acid. The crystal structures of 3-nitro-2-(phenylselanyl)-imidazo[1,2-a]pyridine (5a), 2-(mesitylselanyl)-3-nitro-imidazo[1,2-a]pyridine (5d) and 3-nitro-2-(pyridin-2-ylselanyl)-imidazo[1,2-a]pyridine (5e) were confirmed by X-ray crystallography and the DFT calculations were performed to determine various structural parameters which were correlated with the X-ray crystal structures. The synthesized compounds were subjected to antimicrobial evaluation and it was found that compounds 5a and 5j were active against gram negative bacterium Escherichia coli whereas compound 5e was active against different fungal strains. Time kill assay was performed to understand the microbial activity of synthesized organoselenium compounds and the toxicity of these compounds was evaluated against human cell lines. Synergistic effects of active compounds 5a and 5e were tested with existing antibiotic drugs which exhibited that the antibiotic combination with synthesized organoselenium compounds efficiently enhanced the antimicrobial activity.

Dehydration of Alcohols by Microporous Niobium Silicate AM-11

The dehydration of ethanol, 1-propanol and 1-butanol has been studied at atmospheric pressure using the novel microporous niobium silicate AM-11 (Aveiro–Manchester structure number 11) in the temperature range 150–300 °C. The selectivity for alkenes increases with temperature for all three alcohols and reaches 100% for 100% conversion at 250–300 °C. At lower reaction temperatures (∼200 °C), ethers are also formed and their selectivity decreases markedly with the alcohol size.

Synthesis and characterisation of chromium-substituted ETS-10

A series of microporous chromium-containing ETS-10 (ETCrS-10) with different Cr/Ti molar ratios have been synthesised and characterised by energy dispersive absorption of X-rays (EDAX), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption measurements, diffuse-reflectance ultraviolet spectroscopy (DR-UV), electron paramagnetic resonance (EPR) and 29Si magic-angle-spinning nuclear magnetic resonance (MAS NMR). The diffractograms of the as-synthesised ETCrS-10 materials indicate that the ETS-10 structure has remained intact upon Cr substitution. DR-UV and EPR reveal that the as-prepared ETCrS-10 samples contain Cr3+ in octahedral coordination. The resonances in the 29Si MAS NMR spectra of ETCrS-10 are considerably broader than those of ETS-10 and such a broadening may relate to isomorphous substitution of Cr for Ti in the ETS-10 framework. The acid–base properties of ETCrS-10 materials are responsible for the high dehydrogenation activity in the conversion of isopropanol to acetone and dehydration activity in the conversion of tert-butanol to isobutene. Ethanol oxidation over ETCrS-10 yields acetaldehyde as a main product.

Crystallization of new samarium polyborates.

Rare earth borates are important due to their excellent properties, especially for optics. Here, we report the hydrothermal synthesis and structural determination by single-crystal X-ray diffraction of two new samarium polyborates with layered structures, being constituted by hexaborate chains. These hexaborate chains are connected by samarium polyhedra, forming dense sheets that further interact with each other by hydrogen bonding via isolated boric acid between these sheets. The third phase possesses a three-dimensional framework structure. The thermal stability of selective samples has been studied. The crystallization of samarium borate depends highly on the experimental conditions. Three samarium polyborates have been crystallized in very similar experimental conditions, clearly indicating that new lanthanide borate compounds with tailored structures may be prepared in the future by careful choice of physicochemical conditions.

Entanglement temperature in molecular magnets composed of S-spin dimers

In the present work, we investigate the quantum thermal entanglement in molecular magnets composed of dimers of spin S, using an Entanglement Witness built from measurements of magnetic susceptibility. An entanglement temperature, Te, is then obtained for some values of spin S. From this, it is shown that Te is proportional to the intradimer exchange interaction J and that entanglement appears only for antiferromagnetic coupling. The results are compared to experiments carried on three isostructural materials: KNaMSi4O10 (M=Mn, Fe or Cu).