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Picolinate-based segmented dianionic ligands L12– (5-((4-carboxyphenyl)ethynyl)picolinate) and L22– (5,5′-(ethyne-1,2-diyl)dipicolinate) have been used in the synthesis of the highly robust and luminescent europium(III) coordination polymers [(CH3)2NH2][Eu(H2O)2(L1)2] (1) and [(CH3)2NH2][Eu(L2)2]·H2O·CH3COOH (2). Both 1 and 2 exhibit high selectivity for detection of nitroaromatic compounds since they act as quenchers of the Eu3+ emission. Stern–Volmer plots, using nitrobenzene as a quencher, yielded values of KSV = 150 M–1 and 160 M–1 for 1 and 2, respectively. Luminescence studies in the presence of different metal ions indicate a high selectivity for Fe3+ detection, with KSV values of 471 M–1 and 706 M–1 for 1 and 2, respectively. Both 1 and 2 possess extremely robust extended structures, leading to emissive properties that are stable in a wide pH range., Luminescent europium(III) coordination polymers exhibiting a remarkable robustness have been prepared from ethynyl-bridged picolinate ligands. These compounds can selectively detect nitrobenzene and Fe3+ ions in aqueous medium through luminescence quenching. Furthermore, they present a high stability over a wide pH range that allows their practical use in harsh conditions.

The iron(ii) salt [Fe(bpp)2](isonicNO)2·HisonicNO·5H2O (1) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; isonicNO = isonicotinate N-oxide anion) undergoes a partial spin crossover (SCO) with symmetry breaking at T1 = 167 K to a mixed-spin phase (50% high-spin (HS), 50% low-spin (LS)) that is metastable below T2 = 116 K. Annealing the compound at lower temperatures results in a 100% LS phase that differs from the initial HS phase in the formation of a hydrogen bond (HB) between two water molecules (O4W and O5W) of crystallisation. Neutron crystallography experiments have also evidenced a proton displacement inside a short strong hydrogen bond (SSHB) between two isonicNO anions. Both phenomena can also be detected in the mixed-spin phase. 1 undergoes a light-induced excited-state spin trapping (LIESST) of the 100% HS phase, with breaking of the O4W⋯O5W HB and the onset of proton static disorder in the SSHB, indicating the presence of a light-induced activation energy barrier for proton motion. This excited state shows a stepped relaxation at T1(LIESST) = 68 K and T2(LIESST) = 76 K. Photocrystallography measurements after the first relaxation step reveal a single Fe site with an intermediate geometry, resulting from the random distribution of the HS and LS sites throughout the lattice., A proton migration across a short strong hydrogen bond can be triggered by spin crossover of a remote Fe2+ cation, with the onset of a photoinduced activation energy barrier for proton motion at low temperatures.

The spin crossover salt [Fe(bpp) 2 ](isonicNO) 2 ·2.4H 2 O ( 1 ·2.4H 2 O) (bpp = 2,6‐bis(pyrazol‐3‐yl)pyridine; isonicNO = isonicotinate N‐oxide anion) exhibits a very abrupt spin crossover at T 1 /2 = 274.4 K. This triggers a supramolecular linkage (H‐bond) isomerization that responds reversibly towards light irradiation or temperature change. Isotopic effects in the thermomagnetic behaviour reveal the importance of hydrogen bonds in defining the magnetic state. Further, the title compound can be reversibly dehydrated to afford 1 , a material that also exhibits spin crossover coupled to H‐bond isomerization, leading to strong kinetic effects in the thermomagnetic properties.

International audience; One of the most attractive characteristics of some Prussian blue derivatives is the sensitivity of their magnetic properties to the irradiation with light. In this work photoinduced effects in the (Fe0.2Cr0.8)1.5[Cr(CN)6]·15H2O PBA have been studied by means of X-ray-based spectroscopies and magnetometry. It is found that the photosensitivity of this compound is mostly centred on the Fe cations: the exposure to green light induces a transfer of electrons from them to the Cr that provokes a reversal of the previously existing linkage isomerization and increases the elastic strain caused by the misfit of the unit cells of the Fe–NC–Cr and Cr–NC–Cr sublattices. The green light also quenches the magnetism of the FeII high-spin (HS) ions present in the sample and reduces the magnetic moments of most of the Cr cations except for CrII HS. Our study highlights the important role played by the mismatch between the unit cells of the coexisting sub-lattices in ternary Prussian blue analogues.

The appearance of magnetic order in the (Fe0.2Cr0.8)1.5[Cr(CN)6]·15H2O Prussian blue analogue at low temperature has been investigated by means of synchrotron radiation-based X-ray absorption spectroscopy and X-ray magnetic circular dichroism. With the help of ligand field multiplet analysis we have been able to identify the oxidation states of the metallic cations present in the sample and their evolution with temperature. Our experiments reveal that the appearance of ferromagnetic order is triggered by the transformation of CrIII cations to CrII high-spin caused by a transfer of electrons from the Fe to the Cr resulting in an increase of the magnetic interactions within the (Cr, Cr) sublattice. The misfit strain between the (Fe, Cr) and the (Cr, Cr) moieties that coexist within this ternary material influences the balance of oxidation states and hence the magnetic properties of the metallic ions. Misfit relaxation also plays a role in determining the differences between the surface and the bulk of the material. The measurement of the magnetic moments in those two regions suggests that the surface may have a reduced Curie temperature compared to the bulk.

Bilayers of Prussian blue analogues (PBA) constituted of hard and soft magnets have been fabricated by means of electrochemical deposition. This method affords a good contact between two PBA thin films of nanometer thickness. Complete characterization of the resulting system has been performed, which has allowed the determination of the preservation of the chemical identity of both materials during the electrodeposition and the establishment of a clear interface between them. The magnetic behavior of the bilayer can be explained in terms of an exchange-spring magnet.

In this work we have explored the possibilities to create layered organizations of the Mn 12 single-molecule magnets using the Langmuir–Blodgett technique or attaching these clusters onto a metal surface by preparing self-assembled monolayers (SAMs). In the first part we discuss the use of the Langmuir–Blodgett (LB) technique in order to obtain organized magnetic films formed by monolayers of these clusters. Two strategies have been used with this aim. The first one consists of mixing Mn 12 acetate or benzoate derivatives with an amphiphile, while the second procedure is based on the use of Mn 12 derivatives specifically designed to form LB films. An alternative method is that of preparing self-assembled monolayers (SAMs). Some preliminary results obtained with this method are reported in the second part of the work. To cite this article: M. Clemente-Leon et al., C. R. Chimie 6 (2003).

A new compound, IB-00208, has been isolated from the fermentation broth of an actinomycete isolated from a marine environment. The strain was identified as Actinomadura sp. by its chemical and phylogenetic characteristics. The compound shows cytotoxic activity on tumor cell lines and bactericidal activity against gram-positive bacteria.

A series of ditopic ligands has been synthesized in which terminal 2,2‘-bipyridyl (bpy) groups are connected via an ethynylene group through different sites on the pyridine ring. These terminals ha...

Rigid preorganized multitopic ligands have been designed and synthesized. The Pd(0)-catalyzed cross-coupling reactions between ethynylated derivatives of bipyridine or terpyridine and the corresponding bipyridine or terpyridine halides or triflates provide access to various homo-ditopic, hetero-ditopic, homo-tritopic, and hetero-tritopic ligands bearing acetylene or diphenylacetylene central units in fair to excellent yields. Optimal conditions were found with [Pd(PPh3)2Cl2], CuI in THF and diisopropylamine at rt, or with [Pd(PPh3)4] in benzene and diisopropylamine at 80 °C. When a phenylethynyl group is present in the molecule, the relevant conditions involve [Pd(PPh3)4] in n-propylamine at 60 °C. Oxidative dimerization of the ethynylated derivatives in the presence of cupric salts and oxygen gives the corresponding homo-ditopic ligands bearing diacetylene or diphenyldiacetylene as a spacer in good yields. These methods provide a practical approach to the rational design of multichelating ligands for coo...

Structural, electronic, and magnetic properties of [Mn 12O 12(bet) 16(EtOH) 4](PF 6) 14·4CH 3CN·H 2O (in short Mn 12bet, bet = betaine = +N(CH 3) 3-CH 2-COO -) single-molecule magnets (SMMs) deposited on previously functionalized gold surfaces have been investigated. Self-assembled monolayers (SAMs) either of sodium mercaptoethanesulfonate (MES) or mercaptopropionic acid (MPA) are used as functionalization to avoid the direct interaction between the Mn 12bet molecules and the Au surface with the aim of preserving the main functional properties of the molecules. Scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) analysis show deposited Mn 12bet SMMs well-isolated from each other and uniformly distributed on both MES and MPA SAMs. X-ray absorption spectroscopy (XAS) studies show that the oxidation state of the mixed-valence Mn 12bet core is largely reduced to Mn 2+ when molecules are deposited on MES-SAM, whereas in the case of MPA-SAM the relative weights of Mn 2+, Mn 3+, and Mn 4+ in the Mn 12bet core are preserved. Despite the substantial retaining of their electronic properties, the magnetization of Mn 12bet molecules deposited on MPA-SAM measured by X-ray magnetic circular dichroism (XMCD) is perturbed with respect to the pristine molecules. © 2012 American Chemical Society., Financial support from the European Union (project ELFOS and ERC Advanced Grant SPINMOL to EC), the Spanish MINECO (Project CONSOLIDER on Molecular Nanoscience CSD2007-00010 and Projects CTQ-2008-06720-C02-01/BQU, MAT2007-61584, MAT2009-13977-C03 and MAT2011-22785) and the Generalitat Valenciana (PROMETEO Program) is gratefully acknowledged.

Nanoparticles (NPs) have emerged as a potential tool to improve cancer treatment. Among the proposed uses in imaging and therapy, their use as a drug delivery scaffold has been extensively highlighted. However, there are still some controversial points which need a deeper understanding before clinical application can occur. Here the use of gold nanoparticles (AuNPs) to detoxify the antitumoral agent cisplatin, linked to a nanoparticle via a pH-sensitive coordination bond for endosomal release, is presented. The NP conjugate design has important effects on pharmacokinetics, conjugate evolution and biodistribution and results in an absence of observed toxicity. Besides, AuNPs present unique opportunities as drug delivery scaffolds due to their size and surface tunability. Here we show that cisplatin-induced toxicity is clearly reduced without affecting the therapeutic benefits in mice models. The NPs not only act as carriers, but also protect the drug from deactivation by plasma proteins until conjugates are internalized in cells and cisplatin is released. Additionally, the possibility to track the drug (Pt) and vehicle (Au) separately as a function of organ and time enables a better understanding of how nanocarriers are processed by the organism. The authors acknowledge financial support from the grants “Plan Nacional” (MAT2009-14734-C02-01 and MAT2009-14734-C02-02) and NANOBIOMED-CONSOLIDER (CSD2006-00012) from the Spanish Government. Also grants VALTEC09-2-0085, VALTEC09-2-0089, and 2009-SGR-776 from the Catalan Government SI

The terdentate anionic picolinate-based nitronyl nitroxide (picNN) free radical forms neutral and robust homoleptic complexes with rare earth-metal ions. The nonacoordinated Tb3+ complex Tb(picNN)3• 6H2O is a single-molecule magnet with an activation energy barrier Δ = 22.8 ± 0.5 K and preexponential factor τ0 = (5.5 ± 1.1) × 10-9 s. It shows magnetic hysteresis below 1 K. © 2011 American Chemical Society., We thank the European Union (NoE MagMaNet), Ministerio de Ciencia e Innovación (FEDER financed projects MAT2007-61584 MAT2009-13977-C03 and CONSOLIDER-INGENIO 2010 CSD2007-00010), and Generalitat Valenciana (PROMETEO/2009/095).

5 páginas, 3 figuras, 1 esquema., The effect of solvent isotopic replacement (H for D) on the size of gold nanoparticles (Au NPs) prepared by sodium citrate reduction has been investigated. With increasing replacement of water by deuterium oxide, smaller sizes of Au NPs are obtained, which is interpreted as a consequence of a faster reduction. A mechanism in which a substitution complex, [AuCl3(C6H5O7)−2]−, is formed from AuCl4 and citrate ions prior to its rate-limiting disproportionation into products is suggested. This novel procedure offers an attractive alternative to the existing ones and opens a full range of possibilities for biological studies., The work is supported in part by Ministerio de Ciencia e Innovación under grant numbers PTQ-06-2-0839 (for I.O.-J.) and Consolider Nanobiomed Ingenio 2010.

International audience; This paper is divided into two parts: in the first part, the influence of solvate molecules on the magnetic properties of spin crossover salts of [Fe(bpp)(2)][Cr(L)(ox)(2)]ClO(4) x nS (bpp = 2,6-bis(pyrazol-3yl)pyridine; L = 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen); ox = oxalate dianion; S = solvent) is analyzed. The second part is devoted to the photomagnetic properties of the previously reported [Fe(bpp)(2)][Cr(L)(ox)(2)](2) family of compounds. The study describes the crystal structure, differential scanning calorimetry (DSC) and magnetic properties of [Fe(bpp)(2)][Cr(bpy)(ox)(2)]ClO(4) x EtOH x 4 H(2)O (1) and [Fe(bpp)(2)][Cr(phen)(ox)(2)]ClO(4) x 1.5 EtOH x 4 H(2)O (2). Both salts are high-spin (HS) compounds. Desolvation of 1 yields a material exhibiting a gradual spin crossover that involves 50% of the Fe(2+) cations. Rehydration of this desolvated salt induces a significant increase in the low-spin (LS) population. Desolvation of 2 affords a material showing a more abrupt spin crossover with thermal hysteresis (T(1/2)(increasing) = 286 K and T(1/2)(decreasing) = 273 K). This material is not very sensitive to rehydration. The anhydrous compounds [Fe(bpp)(2)][Cr(bpy)(ox)(2)](2) (3) and [Fe(bpp)(2)][Cr(phen)(ox)(2)](2) (4) display some quantitative photomagnetic conversion with T(LIESST) values of 41 and 51 K, respectively. Kinetic parameters governing the photo-induced HS-LS relaxation process have been determined and used to reproduce the T(LIESST) curves.

Los depósitos de jales inactivos de la Unidad Minera Santa Bárbara fueron estudiados con el objetivo de evaluar su impacto ambiental en suelos y sedimentos de los alrededores. Se analizaron tanto la concentración total de los elementos potencialmente tóxicos (EPT) como la concentración de EPT solubles en agua, con el fin de valorar su potencial de lixiviación para movilizarse y contaminar otros medios abióticos del entorno. Los valores de pH de los jales oxidados resultaron cercanos a la neutralidad, lo que indica que la disolución de minerales con potencial de neutralización consumió la acidez generada por la oxidación de los sulfuros metálicos en estos jales. Los jales contienen altas concentraciones totales de Zn (1,762 – 21,059 mg·kg-1), Pb (972 – 16,881 mg·kg-1), As (410 – 3,281 mg·kg-1) y Cu (472 – 2,415 mg·kg-1). Las concentraciones totales de los otros elementos estudiados en los jales fueron relativamente bajas (Ba: 62 – 586 mg·kg-1, Cd: 10 – 239 mg·kg-1 y Se: 1 – 10 mg·kg-1) e incluso no detectadas por las técnicas de análisis en el caso del Cr, Ni, Hg y Ag. Sin embargo, las concentraciones de los EPT solubles en agua fueron bajas (Zn #8804; 2.0 mg·l-1, Pb 0.07 mg·l-1, As #8804; 0.05 mg·l-1, Cu 0.02 mg·l-1, Cd #8804; 0.2 mg·l-1 y Fe 0.25 mg·l-1). Estas bajas concentraciones de EPT solubles y los valores de pH cercanos a la neutralidad indican un bajo potencial de estos jales para la generación de drenaje ácido. En las muestras de suelos y sedimentos superficiales, ubicadas en los alrededores de las presas de jales, las concentraciones totales de Zn, Pb, Cu, As y Cd fueron mayores a la mediana de los valores de fondo naturales determinados en este estudio (974 mg·kg-1 Zn, 947 mg·kg-1 Pb, 190 mg·kg-1 Cu, 342 mg·kg-1 As y 28 mg·kg-1 Cd). Estos resultados indican que los suelos y sedimentosestán contaminados debido a la dispersión de los jales. Sin embargo, las concentraciones de los EPT solubles en agua fueron bajas: Cu #8804;0.16 mg·l-1 y Cd #8804; 0.005 mg·l-1. Para el caso del Pb, en 39 muestras de un total de 47 (incluidas muestras superficiales y subsuperficales) se registraron concentraciones de Pb soluble en agua inferiores al límite de detección (0.07 mg·l-1), y solamente en ocho muestras se registraron concentraciones de 0.1 a 0.89 mg·l-1. Las concentraciones de As soluble en agua variaron entre 0.0005 y 0.65 mg·l-1 y las de Zn variaron entre 0.02 y 2.85 mg·l-1. La poca disponibilidad de los elementos potencialmente tóxicos es una evidencia de que estos suelos y sedimentos contaminados no representan un riesgo ambiental de consideración bajo las condiciones actuales. Esto se corrobora con el hecho de que en las aguas subterráneas someras se registraron concentraciones muy bajas de elementos potencialmente tóxicos, las cuales son inferiores a los límites señalados para aguas de consumo humano

This paper reports on molecular-based magnetic thin films of Prussian blue analogues (PBA) with high critical temperatures composed of mixed-valence chromium cyanides. The thin films of PBA were synthesized by means of electrodeposition technique. Morphology and magnetic study are presented in a function of electrochemical deposition conditions. We present the electrochemical methods as a promising and effective tool for preparing molecular-based magnetic thin films of Prussian blue analogue.