Unprecedented layered coordination polymers of dithiolene group 10 metals: Magnetic and electrical properties

One-pot reactions between Ni(ii), Pd(ii) or Pt(ii) salts and 3,6-dichloro-1,2-benzenedithiol (HSC6H2Cl2SH) in KOH medium under argon lead to a series of bis-dithiolene coordination polymers. X-ray analysis shows the presence of a common square planar complex [M(SC6H2Cl2S)2]2- linked to potassium cations forming either a two-dimensional coordination polymer network for {[K2(μ-H2O)2(μ-thf)(thf)2][M(SC6H2Cl2S)2]}n [M = Ni (1) and Pd (2)] or a one-dimensional coordination polymer for {[K2(μ-H2O)2(thf)6][Pt(SC6H2Cl2S)2]}n (3). In 3 the coordination environment of the potassium ions may slightly change leading to the two-dimensional coordination polymer {[K2(μ-H2O)(μ-thf)2][Pt(SC6H2Cl2S)2]}n (4) that crystallizes together with 3. The physical characterization of compounds 1-3 show similar trends, they are diamagnetic and behave as semiconductorsWe thank financial support from MICINN (MAT2013-46753-C2-1-P, CTQ2014-52758-P and MAT2014-56143-R) and Generalitat Valenciana (PrometeoII/2014/076

Synthesis and structural characterization of transition metal dithiolene derivatives containing divalent metals as counter-cations

Direct reactions between HSC 6 H 2 Cl 2 SH, FeCl 3 ·6H 2 O and divalent metal bases lead to the formation of the cation-anion metal-dithiolene complexes [Ca(H 2 O) 3 (OCMe 2 ) 4 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ]·3OCMe 2 and [Zn(DMF) 6 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ], as well as the molecular compound [Ba(OCMe 2 ) 6 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ], instead of metal-dithiolene coordination polymers as compared with results previously obtained when alkali metals, under similar conditions, were used. An alternative synthetic route based on the reactions between K 2 [Fe 2 (SC 6 H 2 Cl 2 S) 4 ] and ZnCl 2 ·6H 2 O or NiCl 2 ·6H 2 O was also evaluated, giving rise to the ion-pair compounds [Fe(H 2 O) 2 (THF) 4 ][Ni(SC 6 H 2 Cl 2 S) 2 ] 2 ·4THF and [Fe(H 2 O) 4 (THF) 2 ][Fe 2 (SC 6 H 2 Cl 2 S) 4 ]·4THF and the coordination polymer {[K 2 (THF) 8 ][Zn 6 (μ-Cl) 2 (SC 6 H 2 Cl 2 S) 4 (μ-κO:κO-SC 6 H 2 Cl(ClO 2 )S) 2 ]} n . It is interesting to remark that in the last compound the oxidation of one Cl substituent of a dithiolene ligand resulted in the formation of a Cl(O) 2 groupThis work was supported in part by MICINN (grant MAT2016-77608-C3-1-P

Structural study of the compounds formed in the reactions of FeCl3·6H2O with Ni(OH)2 in the presence of dithiolenes HSRSH (R = C6H2Cl2 or C6H4)

In our attempts to prepare coordination polymers by reaction of FeCl3·6H2O and Ni(OH)2 in the presence of dithiolenes HSC6H2X2SH (X = Cl or H), several ion pairs of compounds containing the anionic entity [Ni(SC6H2X2S)2]⁻ were obtained instead. It was also found that other species without dithiolene ligands were formed in these reactions, giving rise to different ion pairs and a tetrametallic cluster. The careful isolation of the different types of crystalline solids allowed the characterization of all of the resulting compounds by single crystal X-ray diffraction (SCXRD). In order to establish the amount of nickel and iron present in the crystals, complementary total reflection X-ray fluorescence (TXRF) analyses were performed. The eight different structural types that were obtained are described and compared with related ones found in the literaturaThis research was funded by the Spanish Ministerio de Economía y Competitividad, grand number (MAT2016-77608-C3-1-P) and Ministerio de Ciencia, Innovación y Universidades (PGC2018-094644-B-C21

Structural diversity of compounds based on iron-dithiolene with sodium or potassium complexes

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Crystal Growth and Design, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: https://pubs.acs.org/doi/abs/10.1021/acs.cgd.6b00921A series of iron dithiolene compounds with sodium or potassium complexes have been prepared by direct reactions. Their structures consist of coordination polymers of different dimensionalities or molecular compounds depending on the nature of the iron precursor, the presence or not of a donor substituent in the aromatic ring of the dithiolene ligand, and the amount of water molecules present during the crystallization. Since all these compounds are based on the combination of cationic alkaline and anionic iron-dithiolene entities that connect each other by coordination bonds, in order to favor local electroneutrality the structures obtained show that charged entities with a similar charge/size ratio pack more effectively. The flexibility of the potassium coordination environment seems to facilitate the structural diversity found for this family of compounds.Financial support from Spain’s MICINN (MAT2013-46753-C2-1-P and MAT2013-46502-C2-1-P) and Factoría de Cristalización (CONSOLIDER-INGENIO 2010) is gratefully acknowledged

Volatiles and refratories in solar analogs: no terrestial planet connection

We have analysed very high-quality HARPS and UVES spectra of 95 solar analogs, 24 hosting planets and 71 without detected planets, to search for any possible signature of terrestial planets in the chemical abundances of volatile and refractory elements with respect to the solar abundances. We demonstrate that stars with and without planets in this sample show similar mean abundance ratios, in particular, a sub-sample of 14 planet-host and 14 "single" solar analogs in the metallicity range 0.14<[Fe/H]<0.36. In addition, two of the planetary systems in this sub-sample, containing each of them a super-Earth-like planet with masses in the range ~ 7-11 Earth masses, have different volatile-to-refratory abundance ratios to what would be expected from the presence of a terrestial planets. Finally, we check that after removing the Galactic chemical evolution effects any possible difference in mean abundances, with respect to solar values, of refratory and volatile elements practically dissappears.Comment: 2 pages, 2 figures, to appear in the proceedings of the 276th IAU Symposium "The Astrophysics of Planetary Systems

Comparative studies of oxidation processes on Group 10 Metals Dithiolene Derivatives in the formation of coordination polymers

This document is the Accepted Manuscript Version of a Published Work that appeared in final form in "Crystal Growth and Design", copyright © 2018 American Chemical Society after peer review and techical editing by publisher. To access the final and published work see "Comparative Studies of Oxidation Processes on Group 10 Metals Dithiolene Derivatives in the Formation of Coordination Polymers Oscar Castillo, Esther Delgado, Carlos J. Gómez-García, Diego Hernández, Elisa Hernández, Pilar Herrasti, Avelino Martín, and Félix Zamora Crystal Growth & Design 2018 18 (4), 2486-2494Air oxidation of the dithiolene derivatives {[K2(μ-H2O)2(μ-thf)(thf)2][Ni(SC6H2Cl2S)2]}n and {[K2(μ-H2O)2(thf)6][Pt(SC6H2Cl2S)2]}n yielded the ion-pair compounds [K(thf)6][M(SC6H2Cl2S)2] [M = Ni or Pt], while no reaction was observed for the case of {[K2(μ-H2O)2(μ-thf)(thf)2][Pd(SC6H2Cl2S)2]}n. Cyclic voltammetric studies have been used to rationalize this different behavior. Additionally, the new coordination polymers {[K2(thf)8][Ni4(SC6H4S)6]}n, {[K4(thf)4(H2O)2.28][Pd(O2SC6H4S)1.36(OSC6H4S)0.64]2}n, {[K2(H2O)4][Pd(O2SC6H4S)2][Pd(O2SC6H4S)(SC6H4S)]}n, and {[K4(thf)4(H2O)2.24][Pt(O2SC6H4S)1.38(OSC6H4S)0.62]2}n have been obtained using a similar synthetic strategy, i.e., oxidation reactions of group 10 metals dithiolene derivatives bearing (SC6H4S)2– ligandsThis work was supported in part by MICINN (grants MAT2016-77608-C3-1-P, MAT2016-75883-C2-1-P, CTQ2013-44625-R and and CTQ2017-87201-P) and Generalitat Valenciana (PrometeoII/2014/076

Group 10 Metal Benzene-1,2-dithiolate Derivatives in the Synthesis of Coordination Polymers Containing Potassium Countercations

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b01775The use of theoretical calculations has allowed us to predict the coordination behavior of dithiolene [M(SC6H4S)2]2- (M = Ni, Pd, Pt) entities, giving rise to the first organometallic polymers {[K2(μ-H2O)2][Ni(SC6H4S)2]}n and {[K2(μ-H2O)2(thf)]2[K2(μ-H2O)2(thf)2][Pd3(SC6H4S)6]}n by one-pot reactions of the corresponding d10 metal salts, 1,2-benzenedithiolene, and KOH. The polymers are based on σ,π interactions between potassium atoms and [M(SC6H4S)2]2- (M = Ni, Pd) entities. In contrast, only σ interactions are observed when the analogous platinum derivative is used instead, yielding the coordination polymer {[K2(μ-thf)2][Pt(SC6H4S)2]}nThis work was supported in part by the MICINN (grants MAT2016-77608-C3-1-P and MAT2016-75883-C2-1-P), Generalitat Valenciana (PrometeoII/2014/076), and ISIC. J.I.M. acknowledges financial support by the “Ramon y Cajal ́ ” Program of MINECO (RYC-2015-17730

Volatiles and refratories in solar analogs: No terrestial planet connection

We have analysed very high-quality HARPS and UVES spectra of 95 solar analogs, 24 hosting planets and 71 without detected planets, to search for any possible signature of terrestial planets in the chemical abundances of volatile and refractory elements with respect to the solar abundances. We demonstrate that stars with and without planets in this sample show similar mean abundance ratios, in particular, a sub-sample of 14 planet-host and 14 "single” solar analogs in the metallicity range 0.14 < [Fe/H] < 0.36. In addition, two of the planetary systems in this sub-sample, containing each of them a super-Earth-like planet with masses in the range ~ 7-11 Earth masses, have different volatile-to-refratory abundance ratios to what would be expected from the presence of a terrestial planets. Finally, we check that after removing the Galactic chemical evolution effects any possible difference in mean abundances, with respect to solar values, of refratory and volatile elements practically dissappear

Chemical clues on the formation of planetary systems

Theoretical studies suggest that C/O and Mg/Si are the most important elemental ratios in determining the mineralogy of terrestrial planets. The C/O ratio controls the distribution of Si among carbide and oxide species, while Mg/Si gives information about the silicate mineralogy. We find mineralogical ratios quite different from those of the Sun, showing that there is a wide variety of planetary systems which are not similar to Solar System. Many of planetary host stars present a Mg/Si value lower than 1, so their planets will have a high Si content to form species such as MgSiO3. This type of composition can have important implications for planetary processes like plate tectonics, atmospheric composition or volcanism. Moreover, the information given by these ratios can guide us in the search of stars more probable to form terrestrial planet

Estudiantes con discapacidad intelectual y estudiantes de pedagogía reflexionan y diseñan un programa de prevención del acoso escolar

págs.: 35-42Capítulo incluido en el libro: 1ª Jornada sobre Maltrato a las Personas con Discapacidad: Sevilla, 16-17 de Octubre 2014 Sevilla: Universidad Internacional de Andalucía, 2014. ISBN: 978-84-7993-256-5. Enlace: http://hdl.handle.net/10334/337