136 research outputs found

    Chiroptical and magnetic properties of star-shaped Fe-4(III) complexes from chiral Schiff bases. Structural and magnetic correlations based on continuous shape measures

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    New chiral Fe-4(III) star-shaped complexes have been synthesized starting from enantiomerically pure Schiff bases and chiroptically and magnetically characterized. The structural and magnetic properties of the complete family of 40 Fe-4 complexes reported in the literature have been analyzed in the search for synthetic and magnetostructural correlations

    Lithium cations in a self-assembled electrostatic nanocapsule

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    Cascade self-assembly of small components, without the employment of preformed hosts, yielded a {Ni12Li2} nanometric capsule with multiple endo- and exo-guests (water molecules, Li+, and Et3NH+ cations) linked to selective hydrophilic and hydrophobic binding sites of NiII hexanuclear metallamacrocycles. The synthesis was achieved by using (Bu4N)N3 as a starting reagent instead of the conventional sodium azide to selectively introduce the Li+ cations

    2017 MEDAM assessment report on asylum and migration policies in Europe : sharing responsibility for refugees and expanding legal immigration

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    How can the responsibility for refugees be distributed more fairly – globally and within the EU? And how can we curb irregular migration while expanding legal immigration to the benefit of all concerned? The large number of refugees and other migrants who have come to Europe over the last two years has caused the EU member states that received most of the asylum seekers, to reach their capacity limits. With a view to new arrivals and their long-term integration, it is now necessary to develop new and, above all, common strategies to address the migration flows to Europe. The 2017 MEDAM Assessment Report focuses on two core messages: Distribute the responsibility for refugees more equitably and extending legal immigration from non-EU Member States into EU member states.This report was written by a team led by Matthias LĂŒcke and comprising Esther Ademmer, Mehtap AkgĂŒĂ§, Mikkel Barslund, Anna Di Bartolomeo, David Benček, Dominik Groll, Rezart Hoxhaj, Mauro Lanati, Nadzeya Laurentsyeva, Lars Ludolph, Afaf Rahim, Rainer Thiele, Claas Schneiderheinze, Tobias Stöhr, and Alessandra Venturini

    Na2MnIII6 LnIII clusters with a non-equivalent core: chiral vs. meso isomerism

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    A wide family of clusters with the Na2MnIII6 LnIII core derived from an enantiomerically pure or a racemic mixture of Schiff bases lead to the characterization of a unique case of chiral/meso isomers with C3/D3d symmetry respectively, involving the rearrangement of the cluster bond parameters and the change from hepta- to hexacoordination of the central LnIII cation

    Anionic guests in prismatic cavities generated by enneanuclear nickel metallacycles

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    The combination of polydentate aminated ligands with the 2-pyridyloxime-nickel-azide system leads to series of clusters with unprecedented topologies. Among them, a remarkable family of {Ni9} metallacycles that are capable of selective encapsulation of azide/halide anions in a cryptand-like cavity through hydrogen-bond interactions has been characterized

    Linked Nickel Metallacrowns from a Phosphonate/2-Pyridyloximate Blend of Ligands: Structure and Magnetic Properties

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    In the present work, four new NiII clusters with nuclearities ranging between Ni4 and Na2Ni8 were synthesized, employing the versatile ligand phenylphosphonate and 6-methylpyridylaldoximate as the coligand. Crystallographic data show that the tetranuclear complex [Ni 4 (6-MepaoH)4(PhPO3)2(OH)2(MeOH)4](OH)2 (1) consists of two dimers linked by phosphonate bridges, whereas [Cs2Ni6(6-Mepao)6(PhPO3)3(OH)2(H2O)8] (2), Cs[Ni8(6-MepaoH)6(6-Mepao)6(PhPO3)3](ClO4)5 (3), and [Ni8Na2(BzO)6(6-Mepao)6(PhPO3)3] (4) are built from phosphonato-linked {Ni3(6-Mepao)3} metallacycles. The [9-MCNiII(6‑Mepao)-3] fragments in 2−4 show the unusual coordination of additional Cs+, Na+ , and/or NiII cations. Direct-current magnetic measurements were carried in the 300−2 K range. Analysis of the experimental data revealed a complex response with strong antiferromagnetic interactions mediated by the oximato bridges and weak interactions mediated by the phosphonate ones

    Template arrangement of {Ni3(&m3-OH)(SO4)(R-NO)2}+ fragments around Na+ cations: An unprecedented {Ni12Na} unit linked by oximate and sulfate bridges

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    Anovel {−Ni12Na2-Ni-}n chain has been characterized fromthe reaction between 2-pyridylcyanoxime, (pyC{CN}NOH), and nickel(II) sulfate. The template synthesis around a Na+ cation gives an unprecedented arrangement of four nickel triangles coordinated to the central sodium ion by sulfato bridges

    Enhancement of magnetic relaxation properties with 3d diamagnetic cations in [ZnIILnIII] and [NiIILnIII], LnIII=Kramers lanthanides

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    Employing the chiral bi-compartmental Schiff-base ligand H2L obtained from the condensation of (RR) or (SS)-1,2-diphenyl-ethylenediamine and o-vanillin, we report the structural characterization of the discrete dinuclear pairs of enantiomers [NiIIEuIII] 1RR, 1SS and [ZnIIEuIII] 2RR, 2SS and the magnetic properties for the series of complexes [NiIILnIII], Ln = Ce, 3RR; Nd, 4RR; Dy, 5RR; Er, 6RR, Yb, 7SS and [ZnIILnIII], Ln = Ce, 8RR; Nd, 9RR; Dy, 10SS; Er, 11SS and Yb, 12RR in which MII is diamagnetic and LnIII is a Kramers lanthanide. Single crystal X-ray diffraction shows that relevant changes in the [ZnIILnIII] structures are produced after a period in open air (2RRb, 2RRc), evidencing that the lability of the ligands bonded to ZnII can modify the structures that will be correlated to the experimental measurements. The dynamic magnetic measurements showed that the [NiIILnIII] and [ZnIILnIII] derivatives exhibit different behaviors in the relaxation of magnetization especially for oblate and prolate LnIII cations

    Decanuclear FeIII clusters with hemiacetal ligands: a new{M10(Ό3-O)8} cluster core

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    The characterization of a decanuclear FeIII cluster with α-methyl- 2-pyridinemethanolate, generated by the hydrolysis of Schiff bases, inspired us to carry out an initial exploration of the direct syntheses of medium nuclearity FeIII clusters starting from aldehydes in methanolic medium. The new complexes exhibit an unprecedented {Fe10(Ό3-O)8} cluster core

    Chiral Oxazolidine Complexes Derived from Phenolic Schiff Bases

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    Schiff bases derived from pyridyl- or salicyl-aldehydes and aminoalcohols can evolve to heterocyclic oxazolidines, which in the presence of cations allow the formation of uncommon coordination compounds. In this work, we report new NiII and mixed valence MnII/ MnIV complexes derived from pyridyl oxazolidines and the unprecedented characterization of enantiomerically pure oxazolidines derived from the condensation of o-vanillin with phenylglycinol in the presence of NiII cations. The different reactivity of the pyridinic or phenolic Schiff bases has been compared, and the new systems have been structurally, optically, and magnetically characterized
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