TITLE [BOLD, CAPITAL LETTERS] · SYMPOSIUM "1er SIMPOSIO INTERNACIONAL DEL LIA MIF 836 EN QUÍMICA...

1

SYMPOSIUM

1er Simposio

Internacional del LIA MIF

836 en Química de

Coordinación y

Materiales InorgánicosVa

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LIBRO DE RESÚMENES

SYMPOSIUM

"1er SIMPOSIO INTERNACIONAL DEL LIA MIF 836 EN QUÍMICA DE

COORDINACIÓN Y MATERIALES INORGÁNICOS"

Libro de Resúmenes

Valparaíso - Chile, 10 y 11 de Enero de 2013

AGRADECIMIENTOS

El Comité Organizador del Simposio agradece el Patrocinio y Auspicio de los siguientes

Organismos e Instituciones

http://www.cnrs.fr/

PRESENTACIÓN

La creación del Laboratorio Internacional Asociado “Materiales Inorgánicos

Funcionales” (LIA MIF 836), impulsado por el prof. Jean-Yves Saillard de la

Universidad de Rennes 1, Francia, se materializa en Septiembre de 2009 mediante la

firma del primer contrato cuatrienal establecido entre siete universidades chilenas

(PUCV, UCHILE, USACH, UDEC, UCN, UCM, UNAB) con el Centre National de la

Recherche Scientifique (CNRS), la Universidad de Rennes 1 (UR1) y la Escuela

Nacional Superior de Química de Rennes (ENSCR).

En este contexto, el "1er SIMPOSIO INTERNACIONAL del LIA MIF en QUÍMICA

de COORDINACIÓN y MATERIALES INORGÁNICOS", que se llevará a cabo en la

ciudad de Valparaíso, representa la actividad de clausura del primer contrato, periodo en

el cual los diversos grupos de investigación, constituidos por investigadores chilenos y

franceses, han desarrollado una fructífera labor que se ha traducido en publicaciones en

revistas de corriente principal, con comité editorial, comunicaciones orales y posters en

congresos nacionales e internacionales, y en intercambios de investigadores y de

estudiantes de doctorado. Tales acciones, sin duda, fortalecen la cooperación

internacional entre los grupos participantes como, asimismo, promueven el surgimiento

de nuevas colaboraciones y, más importante aún, la realización de tesis en co-tutela.

Durante estos dos días, en pleno verano chileno, investigadores y estudiantes de

doctorado que han dado cuerpo a esta cooperación internacional, se reúnen para exponer

una parte de los resultados obtenidos en común. También tenemos el honor de contar

con la presencia del Director Científico del Instituto de Química del CNRS y del

Director de Postgrado del Instituto de Química de la P. Universidad Católica de

Valparaíso, como conferencistas invitados.

CONICYT, a través de su Departamento de Relaciones Internacionales, así como el

CNRS, la UR1, la ENSCR y la Embajada de Francia en Chile, han mostrado su

compromiso con este Laboratorio al aportar importantes recursos anuales al LIA MIF,

los que claramente han facilitado la realización de las actividades antes señaladas. No

obstante lo anterior, se requiere un mayor compromiso, particularmente de las

instituciones chilenas involucradas, en consideración a que la renovación por 4 años

(2013-2016) del contrato LIA MIF plantea nuevos desafíos al Laboratorio y a sus

integrantes, desafíos que deben propender al establecimiento de redes multi-grupales, al

incremento en el número de tesis en co-tutela y en el número de pasantías estudiantiles

bilaterales. Decididamente, la concreción de estos desafíos impactará muy fuertemente

en la formación de nuestros estudiantes y en la calidad de la investigación desarrollada.

Diez años después del Simposio PICS N° 922 (7-9 enero de 2003), primera etapa de la

estructuración de la cooperación científica en química entre los dos países, la Pontificia

Universidad Católica de Valparaíso, en el año de su octagésimo quinto aniversario, les

da a todos los participantes la más cordial bienvenida.

COMITÉ ORGANIZADOR

AVANT-PROPOS

Le “1ER SYMPOSIUM INTERNATIONAL DU LIA-MIF EN CHIMIE DE

COORDINATION ET MATERIAUX INORGANIQUES”, qui se tiendra à Valparaiso

(Chili) les 10 et 11 janvier 2013, clôturera le premier contrat quadriennal du Laboratoire

International Associé franco-chilien en chimie intitulé Matériaux Inorganiques

Fonctionnels» (LIA MIF 836), dont la convention de création avait été signée le 03

septembre 2009 au siège du Centre National de la Recherche Scientifique (CNRS) à

Paris (France), entre d’une part le CNRS, l’Université de Rennes 1 (UR1) et l’Ecole

Nationale Supérieure de Chimie de Rennes (ENSCR), et d’autre part, sept universités

chiliennes partenaires (PUCV, UCHILE, USACH, UDEC, UCN, UCM, UNAB).

Durant les quatre années de vie du programme, plusieurs groupes de recherche

constitués par des chercheurs français et chiliens, ont développé une fructueuse activité

scientifique qui s'est traduite par une vingtaine de publications co-signées dans des

journaux internationaux à comité de lecture, des conférences invitées et des

communications orales et par affiche dans des congrès nationaux et internationaux, et

par des échanges de chercheurs et d’étudiants de doctorat entre les deux pays. Nul doute

que de telles actions ont contribué à renforcer la coopération internationale entre les

différents groupes, à favoriser de nouvelles collaborations, et plus important encore, à la

réalisation de thèses en co-tutelle, et ceci malgré le terrible tremblement de terre du 27

février 2010 qui avait très sérieusement affecté nos collègues de l’université de

Concepcion dont certains laboratoires de recherche avaient été totalement détruits.

Durant ces deux journées, au coeur de l'été chilien, les chercheurs et doctorants qui ont

donné corps à cette coopération internationale d’envergure en développant ses multiples

facettes, se rencontrent pour exposer une partie des résultats obtenus en commun. Nous

aurons aussi l’honneur d’accueillir le Directeur Scientifique de l’Institut de Chimie du

CNRS qui présentera la conférence inaugurale, et le plaisir d’ouvrir les portes de ce

Symposium LIA MIF à tous nos autres collègues chiliens qui présenteront leurs travaux

en liaison avec la thématique du Symposium.

Les tutelles françaises signataires (CNRS, UR1 et ENSCR), Rennes Métropole, la

CONICYT chilienne au travers de son département des relations internationales, et

l’Ambassade de France au Chili ont montré tout l’intérêt qu’ils portaient à

l’épanouissement de ce LIA MIF en lui apportant les ressources financières nécessaires

lui permettant de mener à bien ses projets. L’ensemble de ces organismes et les sept

universités chiliennes partenaires viennent de témoigner leur confiance dans cette

aventure humaine et scientifique en renouvelant le LIA MIF pour un nouveau contrat

quadriennal 2013-2016 dont la signature aura lieu durant le Symposium. Qu’ils en

soient ici remerciés. Avec ce renouvellement, ce sont de nouveaux défis qui sont lancés

au LIA MIF et à tous ses membres, comme par exemple, la mise en place de

collaborations multi-croisées en réseau, l’augmentation du nombre de thèses en co-

tutelle et d’échanges bilatéraux d’étudiants de Master et de doctorants.

Dix ans après avoir accueilli le Symposium PICS (7-9 janvier 2003), première étape de

la structuration de la coopération scientifique en chimie entre les deux pays, la

Pontificia Universidad Católica de Valparaíso dans l'année de son quatre-vingt-

cinquième anniversaire, souhaite a tous les participants la plus cordiale bienvenue.

PROGRAMA DE ACTIVIDADES

Jueves 10 de Enero de 2013 14:00 – 15:00 Inscripciones 15:00 – 15:15 Inauguración 15:15 – 16:15 Conferencia Inaugural:

“Phosphorus and organometallic materials for optoelectronic applications” Prof. Régis Réau

16:15 – 16:30 Firma Renovación Contrato LIA MIF 16:35 – 17:30 Cocktail 17:30 – 17:50 Comunicación Oral 1 17:50 – 18:10 Comunicación Oral 2 18:10 – 19:10 Posters

Viernes 11 de Enero de 2013 09:30 – 10:30 Conferencia Invitada:

“Cyclopentadienyl rhenium complexes functionalized with electro-donor groups and biological molecules” Prof. Hugo Klahn

10:30 – 10:50 Comunicación Oral 3 10:50 – 11:10 Comunicación Oral 4 11:10 – 11:30 Break 11:30 – 11:50 Comunicación Oral 5 11:50 – 12:10 Comunicación Oral 6 12:10 – 12:30 Comunicación Oral 7 12:30 – 12:50 Comunicación Oral 8

13:00 – 15:00 Almuerzo 15:00 – 15:20 Comunicación Oral 9 15:20 – 15:40 Comunicación Oral 10 15:40 – 16:00 Comunicación Oral 11 16:00 – 16:20 Comunicación Oral 12 16.20 – 16.40 Break 16:40 – 17:10 Clausura

CONFERENCIAS INVITADAS

Phosphorus and organometallic materials for optoelectronic applications

J. C rassous, M . H issler , C . L escop, R . Réau

Université de Rennes1, CNRS, UMR 6226, Sciences Chimiques de Rennes, campus de Beaulieu, 35042

Rennes cedex [email protected]

http://www.scienceschimiques.univ-rennes1.fr/equipes/om2/phosphore-materials-molecular

-Conjugated oligomers and polymers based on aromatic heterocyclopentadienes have attracted strong interest in recent years owing to their potential applications for electronic devices (light emitting diodes, thin film transistors, photovoltaïc cells...). The tailoring of these semi-conducting organic materials for improving their electrochemical and optical properties towards plastic electronic applications necessitates extensive experimental molecular engineering. We have showed that the phosphole unit is an appealing building block for this molecular engineering due to its low aromatic character and the versatile reactivity of its P-centre that allow a structural diversity to be easily generated. The synthesis of -conjugated systems based on phosphole synthons and their use as materials for OLEDs, including white-emitting devices, will be presented.1 The synthesis of the first P-modified polycyclic aromatic hydrocarbon will be described.2 Their coordination chemistry was also exploited towards the design of new helicenes derivatives with tuneable, large chiroptical properties.3 The versatility of organometallic chemistry for generating structural diversity in helicene chemistry will also be illustrated with the synthesis of helical derivatives including metal centers that act as chiroptical switches.4

References (1) Adv. Mat., 2009, 21, 1261; Chem. Eur. J., 2010, 16, 11340 and 2010, 16, 7143; Adv. Funct. Mat., 2012, 22, 567; Angew. Chem. Int. Ed., 2012, 51, 214; Chem. Eur. J., 2012, 1, 214. (2) J. Am. Chem. Soc., 2012, 15, 6524. (3) Chem. Commun., 2012, 53, 6705; Angew. Chem. Int. Ed., 2012, in press. (4) J. Am. Chem. Soc., 2009, 131, 3183; Angew. Chem. Int. Ed., 2010, 49, 99; Chem. Eur. J., 2011, 17, 14178; J. Am. Chem. Soc., 2011, 133, 3800 ; J. Am. Chem. Soc., 2012, 134, 15628.

http://www.scienceschimiques.univ-rennes1.fr/equipes/om2/phosphore-materials-molecular

mailto:[email protected]

Cyclopentadienyl rhenium complexes functionalized with electro-donor groups and biological molecules

A . Hugo K lahn

Instituto de Química, Pontificia Universidad Católica de Valparaíso, Chile. E-mail: [email protected].

Transition metal complexes containing cyclopentadienyl ligands substituted with electron-donor groups have been of great interest in the last few decades.1 More recently, the involvement of cyclopentadienyl fragments in biological molecules have catalyzed the development of Bioorganometallic Chemistry.2 In both type of compounds ferrocenyl fragment has been by far the most extensively studied not only from their synthetic and structural aspects but also from their applications in catalysis, material science and drugs modification, to name some examples.3

Taking into account that ferrocenyl and cyrhetrenyl fragments are isoelectronic (d6 configuration) but with opposite electronic effects (ferrocenyl is an electron-donor whereas cyrhetrenyl is an electron-acceptor) we decided to carry out a comparative study of compounds containing these fragments. On this context, we would like to present some synthetic and structural aspects of a series of metalloligands with cyrhetrene substituted with functionalities such as: phosphines, imines, pyridine, polipyridine and β-diketones, as well as their transition metal complexes.4,5

With regard to bioorganometallic compounds, we will show the synthesis and characterization of a new family compounds with potential antichagasic activity by combination of ferrocenyl and cyrhetrenyl groups with pharmacophores like 5-nitrofurane, 5-nitrothiophene and thiosemicarbazides.6 We will also include a series of cyrhetrenyl chalcones with potential antimalarial activity.7

References 1.- P. Jutzi, C. Muller, D. Vos; J. Organomet. Chem. 2000, 600, 127 2.- G. Jaouen (Ed.) Bioorganometallics: Biomolecules, Labeling, Medicine, Wiley- VCH, 2006. 3.- P. Stepnicka (Ed.) F errocenes: Ligands, Material and Biomolecules, Wiley, 2008. 4.- D. Sierra, A. H. Klahn, R. Ramirez-Tagle, R. Arratia-Perez, F. Godoy, M. T. Garland, M. Fuentealba, Dalton Trans. 2010, 39, 6295 5.- T. Cautivo, H. Klahn, F. Godoy, C. Lopez, M. Font-Bardía, T. Calvet, E. Gutierrez-Puebla, A. Monge; Organometallics 2011,30, 5578. 6.- R. Arancibia, A. H. Klahn, G. E. Buono-Core, E. Gutierrez-Puebla, A. Monge, , M. E. Medina, C. Olea-Azar, J. D. Maya, F. Godoy; J. Organomet. Chem. 2011, 696, 3238. 7.- R. Arancibia, C. Biot, G. Delaney, P. Roussel, A. Pascual, B. Pradines, A. H. Klahn; J. Organomet. Chem. 2013, 723, 143


COMUNICACIONES ORALES

O 1 Evaluación de las propiedades O N L de nuevos comple jos metálicos de

bases de Schiff asimétr icos del tipo A-π-D

a Salvador Celedón, a Carolina Manzur , a David Carrillo, b Jean-René Hamon, a Mauricio Fuentealba.

a Laboratorio de Química Inorgánica, Facultad de Ciencias, Pontificia Universidad Católica de

Valparaíso. Avenida Universidad 330. Curauma , Valparaíso, Chile. b UMR 6226 Sciences Chimiques de Rennes, CNRS-Université de Rennes 1, Campus de Beaulieu. 35042

Rennes Cedex, F rance. e-mail: [email protected],[email protected]

El diseño de complejos asimétricos que actúen como cromóforos dipolares del tipo “push-pull”, ha sido un desafío para el campo de la química de coordinación en los últimos años, debido a que éstos pueden considerarse como materiales potencialmente útiles en la fabricación de: procesadores ópticos, dobladores de frecuencia láser, interruptores ópticos, entre otros.1 Es por ello que en este trabajo se presentan nuevos complejos de bases de Schiff asimétricos de Co(II), Ni(II), Cu(II) y Pd(II), con tres distintos grupos aceptores de electrones, a saber, [Cp*Ru]+, -NO2 y -COOH (figura 1). Estas tres familias de complejos han permitido evaluar el efecto, tanto del centro metálico como del grupo aceptor, sobre sus propiedades Opticas no Lineales de Segundo Orden (ONL-2). Por otra parte, los complejos descritos se muestran como una excelente alternativa para ser incorporados, mediante una reacción de condensación, a una matriz polimérica de cadena principal o lateral,2 a través de la funcionalidad -OH presente en sus estructuras.

Fe

O

N N

O

M

NO2

OH

Fe

O

N N

O

M

OH

Ru PF6

Fe

O

N N

O

M

OH

COOH

M = Co(II) y Ni(II) M = Co(II), Ni(II), Cu(II) y Pd(II) M = Ni(II) y Cu(II)

Figura 1. Complejos base de Schiff asimétricos. Referencias 1. a) M. Fuentealba, J-R. Hamon, D. Carrillo, C. Manzur, New J Chem. 2007, 31, 1815. b) A. Trujillo, M. Fuentealba, D. Carrillo, C. Manzur, I. Ledoux-Rak, J-R. Hamon, J-Y. Saillard, Inorg. Chem. 2010, 49, 2750. 2. a) A. Bilici, I. Kaya, M. Sacak, J. Inorg. Organomet. Polym. 2009, 20, 124. b) A.S. Abd-El Aziz, S. Sezgin, L. Bichler, Eur. Polym. J. 2012, 48, 1901. Agradecimientos: Los autores agradecen al proyecto FONDECYT 1090310, al Laboratorio Internacional Asociado (LIA MIF N°836) y a la Vicerrectoría de Investigación y Estudios Avanzados de la P. Universidad Católica de Valparaíso. S.C. agradece a CONICYT por beca de doctorado, apoyo de tesis y a la Embajada de Francia en Chile por el financiamiento otorgado para la realización de estadía doctoral.

mailto:[email protected],[email protected]

O 2 EPR Spectroscopy as a tool to study mixed valence states of

polyoxovanadoborates

Patricio H ermosilla-Ibáñez,a,b Juan Costamagna,a Carolina A liaga,a,b Ricardo C . Santana,c E ric L e Fur ,d,e Olivier Cador ,f Evgenia Spodine,b,g

Diego Venegas-Yazigi.a,b

a) Facultad de Química y Biología, Universidad de Santiago de Chile, Santiago, Chile. USACH , E-mail:

[email protected] ; b) CEDENNA, Chile.

c) Instituto de F ísica, Universidade F ederal de Goiás, Campus Samambaia, CP 131, 74001-970, Goiânia (GO), Brazil.

d) ENSCR, CNRS, UMR 6226, Rennes, F rance. e) Université Européenne de Bretagne, F rance.

f) Univ Rennes 1, CNRS, UMR 6226, UR1,Inst Sci Chim Rennes, F -35042 Rennes, F rance g) Facultad de Ciencias Químicas y Farmacéuticas. Universidad de Chile, Santiago, Chile.

During the last decade, a new family of polyoxometalates, called polyoxovanadoborates has been reported in the literature. These polyanions present a rich structural variety, due to the different ratios of vanadium/boron that can be obtained. On the other hand, boron can adopt two different geometries (trigonal and tetrahedral) enhancing the condensation possibilities. From the electronic point of view, they can present different ratios VIV/VV.[1] The number of paramagnetic centres in the structure (VIV, 3d1) is determinant of the observed magnetic properties. In this work the study of several compounds, which present the polyanion [V12B18O60H6]n-, with different mixed valence ratios using Electron Paramagnetic Resonance (EPR) is presented. All studied compounds present a single signal (Fig 1); the with and the area of the signal is dependent of the mixed valence ratio.

Figure 1. Compound K5(H3O)2(1,3-diapH2)2[V12B18O60H6]·10.8H2O.

Reference [1] P. Hermosilla-Ibañez, P. E. Car, A. Vega, J. Costamagna, F. Caruso, J.-Y. Pivan, E. Le Fur, E. Spodine, D. Venegas-Yazigi, CrystEngComm., 2012, 14, 5604-5612. Acknowledgements Authors acknowledge FONDECYT 1120004 and Financiamiento Basal Program FB0807 for partial financial support. The authors also thank ECOS-CONICYT C08E02 International Project. This work was done under the LIA-MIF CNRS 836 Collaborative Program. PHI thanks MECESUP UCH 0601 Doctoral Scholarship and AT-24100222 CONICYT.


O 3 Structure and properties of Cu(I) and Ag(I) clusters stabilized by

inorganic ligands: A D F T investigation

Samia K A H L A L

Institut des Sciences Chimiques de Rennes, CNRS-Université de Rennes 1, 35042 Rennes cedex, F rance. [email protected]

Copper(I) and silver(I) are known for their ability to form, in association with various types of bridging and terminal ligands, polynuclear (cluster) species of various shapes and sizes where weak bonding interactions between the closed-shell metal centers is generally present. Associated with this weak interaction, is the presence of one or several unoccupied metallic orbitals of bonding character. These orbitals can be involved in two different phenomena; (i) photoluminescence, especially in the presence of π-donor ligands on the metals, (ii) encapsulation of various anions (including hydrides, see figure 1) inside the cluster cage. In this talk, we give an overview of what can be done with the help of DFT calculations to rationalize the structure and optical properties of Cu(I) and Ag(I) clusters stabilized by π-donor ligands.

Figure 1: [Cu8 (H){Se2P(OiPr)2}6]

+: The first example of a hydride encapsulated into a copper cluster.

References: C. W. Liu et al., J. Am. Chem. Soc. 131, 2009, 11222. C. W. Liu et al., Inorg. Chem, 50, 2011, 8410. C. W. Liu et al., Inorg. Chem, 51, 2012, 6577


O 4 E lectronic properties of polyoxovanadoborates of different nuclearities

K arina Muñoz-Becer ra(a,b), Andrés Vega(b,c), E ric L e Fur(d,e), Jean-Yves

Saillard(d,f), Samia K ahlal(d,f), Diego Venegas-Yazigi(a,b).

a) Facultad de Química y Biología, Universidad de Santiago de Chile, USACH, Santiago, Chile.

[email protected], [email protected] b) CEDENNA, Santiago, Chile

c) Universidad Andrés Bello, Departamento de Ciencias Químicas, Santiago, Chile. d) ENSCR, CNRS, UMR 6226, Rennes, France.

e) Université Européenne de Bretagne, France f) Université de Rennes 1, CNRS, UMR 6226, Rennes, France

The condensation between {MOx}n entities (where M is typically Mo, V and W

atoms, and x can take values from 4 to 7) gives high nuclearity structures called Polyoxometalates (POMs) [1,2], which are highly symmetrical with quasi-spherical morphologies. The inclusion of heteroatoms as boron in polyoxovanadates structures {VOx}n, gives polyoxovanadium-borates (VBO). The vanadium centers in this structures can present mixed-valence states with different VIV/VV relations giving interesting electronic and magnetic properties, due to the delocalization of unpaired electrons between the vanadium centers.

In the present work three new compounds of the VBO family, (NH3CH2CH2CH2NH3)4[V6B20O50H8]·8H2O (1), (NH3CH2CH2NH3)3K2[V6B20O50 H8]·7H2O (2), and (NH3CH(CH3)CH2NH3)6(H3O)2[V10B28O74H8]·28H2O (3) are presented. This three compounds are based on two anion clusters with different nuclearity, [V6B20O50H6]8- and [V10B28O74H8]14- (Figure 1). The compounds were obtained by a molten boric acid flux method, which has been a very efficient method to obtain products with high purity and good yields. The vanadium centers are penta-coordinated adopting a square-pyramidal coordination environment. Based on the valence bond sum calculation (BVS) [3], the mixed-valence ratio VIV/VV for compounds (1) and (2) is 6VIV/0VV and for (3) is 8VIV/2VV. All these compounds have been studied by thermogravimetric analysis (TGA), diffuse reflectance (UV/Vis/NIR) and by electronic paramagnetic resonance (EPR).

References [1] Pope, M. T.; Müller, A. Angew. Chem. Int. Ed. Engl. 1991, 30, 34; Müller, A.; Pope, M.; Gatteschi, D. Chem. Rev. 1998, 98, 239. [2] Robin, M. B.; Day, P. Adv. Inorg. Chem. Radiochem. 1967, 10, 247. [3] I. D. Brown and D. Altermatt. Acta Cryst. 1985, B41, 244. Acknowledgment: The authors thanks to FONDECYT 1120004 and to the Basal Funding FB0807. This work was done under the LIA-MIF CNRS 836 Collaborative Program. KMB thanks to Beca de Doctorado Nacional 21100772, CONICYT, and to Beca de Apoyo de Tesis 24121391, CONICYT.

F igure 1. F igure 1.a. Polyanion [V6B20O50H6]8- of (1) y (2); F igure 1.b. Polyanion [V10B28O74H8]14- of (3).



O 5 T ransition metal complexes containing tr identate Schiff base electron

donor ligands, precursors of new push-pull adducts with potential second order non-linear optical response.

N . Novoaa, D . Car rilloa, C . Manzura, J.-R . Hamonb

aInstituto de Química. Facultad de Ciencias. Pontificia Universidad Católica de Valparaíso. Avenida

Universidad 330. Curauma. Valparaíso. Chile bUMR 6226 ‘‘Sciences Chimiques de Rennes’’, CNRS-Université de Rennes 1, Campus de Beaulieu,

35042 Rennes Cedex, F rance e-mail: [email protected]

Transition metal complexes derived from Schiff base (SB) ligands have attracted considerable interest because of its potential as functionalizable ligands and versatility, two important features in the design and construction of new materials for the optoelectronics1-3. In recent years several transition metal complexes containing asymmetric N2O2 tetradentate SB ligands, containing strong electron donors and acceptors groups as push-pull chromophores, have been reported2,3, in order to get a good second order nonlinear optical response2,3. In the present work we describe the progresses in the synthesis, characterization and study by DFT calculations of a new type of ONO tridentate SB ligand substituted by electron donating groups, (–C6H4-p-OMe) and –[(5-C5H4)Fe(5-Cp)], and their corresponding complexes of late transition metals derivatives (see figure 1 and 2), as potential precursors for the preparation of new dipolar push-pull adducts. The substitution of the pyridine ligand in each of these ONO complexes by a 4,4’-bipyridine ligand is the necessary step to form the dipolar push-pull adducts (see scheme 1). References: 1 Di Bella, S., Chem. Soc. Rev., 2001, 30, 355. 2 Rigamonti, L.; Demartin, F.; Forni, A.; Righetto, S.; Pasini, A., Inorg. Chem. 2006, 45, 10976. 3 Trujillo, A.; Fuentealba, M.; Carrillo, D.; Manzur, C.; Ledoux-Rak, I.; Hamon J.-R.; Saillard. J.-Y., Inorg. Chem., 2010, 49, 2750. Acknowledgments: The authors thank FONDECYT, the funding provided through Project No. 1090310, the LIA-MIF N° 836, the Agreement CONICYT-CNRS, and the Vice-Rectoría de Investigación y Estudios Avanzados, Pontificia Universidad Católica de Valparaíso. N. N. thanks CONICYT for granting doctoral scholarship and the Embassy of France for the 2011 scholarship awarded doctoral internship.

F igure 1. ORTEP of an ONO SB complex of Cu(II) containing a ferrocenyl donor substituent group. Thermal ellipsoids are drawn at 50% probability.

F igure 2. ORTEP of an ONO SB complex of Ni(II) containing a p-MeO-C6H4- donor substituent group. Thermal ellipsoids are drawn at 50% probability.

Scheme 1. New dipolar push-pull adducts


O 6 Physical properties of quaternary chalcogenides with adamantine-like

structure

Fernanda López-Vergaraa, Antonio Galdámeza, V íctor Manríqueza, Patricia Barahonab, O ctavio Peñac

a Departamento de Química, Facultad de Ciencias, Universidad de Chile, Santiago, Chile

b Facultad de Ciencias Básicas, Universidad Católica del Maule, Talca , Chile c UMR 6626 Institut des Sciences Chimiques de Rennes, Université de Rennes 1, Rennes, F rance

A new family of Cu2MII

1-xM’IIxSnS4 (MII = Mn2+, Fe2+, Co2+) chalcogenides has been synthesized by conventional solid-state reactions at 850 °C. The reaction products were characterized by powder X-ray diffraction (XRD), energy-dispersive X-ray analysis (SEM-EDS), Raman spectroscopy and magnetic susceptibility. The crystal structures of Cu2Mn0.2Fe0.8SnS4, Cu2Co0.6Mn0.4SnS4, Cu2Co0.8Mn0.2SnS4, Cu2Fe0.4Co0.6SnS4 and Cu2Fe0.6Co0.4SnS4 have been determined by single-crystal X-ray diffraction. These phases crystallize in the tetragonal kësterite-type structure (space group I-4). The distortions of the tetrahedral volume were calculated and compared with the corresponding differences in the Cu2MIISnS4 (stannite-type) end-member. The compounds show nearly the same Raman spectral features. Temperature-dependent magnetization measurements (ZFC/FC) and high-temperature susceptibility indicate that these solid solutions are antiferromagnetic [1]. These ceramics have dielectric relaxation phenomena.

[1] Fernanda López-Vergara, Antonio Galdámez, Víctor Manríquez, Patricia Barahona, Octavio Peña Journal of Solid State Chemistry 198 (2013) 386–391

*This work has been supported by ECOS-CONICYT (Action CO9E01). This research has been performed as part of the Chilean-French “Joint Laboratory for Inorganic Functional Materials” (LIAMIF).

O 7 Hydroesterification of olefins. Catalysts palladium(I I) containing

nitrogen-phosphorus ligands. Preliminary studies on biphasic homogeneous systems.

Gabriel Abarcaa, Camila Negrete-Vergaraa, B raulio A randaa, Sergio A . Moyab,

Matías V idalb, Pedro Aguir rea

a Universidad de Chile, Facultad de Ciencias Química y Farmacéuticas, Casilla 233, Santiago de Chile,

Chile b Universidad de Santiago de Chile, Facultad de Química y Biología, Avda. Libertador Bernardo

O’Higgins 3363, Santiago de Chile, Chile.

The homogeneous catalysis is an important tool for organic products such as aldehydes, acids and esters. Several research groups in recent years has focused on the task of developing new organometallic compounds with carbene, phosphorus, nitrogen and other types of ligands. During the last time our research group has developed the synthesis and characterization of compounds of ruthenium and palladium containing nitrogen-phosphorus ligands to be applied as homogeneous catalysts in various reactions of interest. The complexes and ligands were synthesized by Schlenk techniques and characterized by nuclear magnetic resonance and elemental analysis [1.2]. Here we reports on the application of compounds of palladium (II) as catalysts in the reaction of hydroesterification of olefins. The catalysis were performed under homogeneous conditions and biphasic medium [3.4].

The authors acknowledge the financial support of FONDECYT-Chile (No. 1120149). LIA-MIF Project No 836, Chile, France and ECOS-CONICYT No. C07E. G. A. thanks CONICYT for doctoral fellowship (No. 21090186) and the grant of theses (No. 24110005). G. A. also thanks the Vice-Rector Academic of the University of Chile. [1] S.A. Moya, M. Vidal, G. Abarca, C. Martinez, R. López, R. Baggio, M. T. Garland, S. Rodriguez, P. Aguirre. Inorg. Chem. Commun. 2011, 13, 1519. [2] P. Aguirre, C. Lagos, S. A. Moya, C. Zuñiga, C. Vera-Oyarce, J. C. Bayón. E. Sola. Dalton Trans. 2007, 46, 5419. [3] C. Zúñiga, S.A. Moya, M. Fuentealba, B. Aranda, P. Aguirre. Inorg. Chem. Commun. 2011, 14, 964. [4] S.A. Moya, M. Vidal, K. Brown, C. Negrete-Vergara, G.Abarca, P. Aguirre. Inorg. Chem. Commun. 2012, 22, 146.

O 8 New synthetic strategies to photoswitches and phosphorescent metal

complexes

V . Guerchais,a M . Zaarour,a K . Beydoun,a J. Boixel,a J. A . G . Williams,b H . L e Bozec,a H . Doucet a

aInstitut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1 35042 Rennes

Cedex, F rance. E-mail: [email protected] bDepartment of Chemistry, Durham University, South Road, Durham, UK DH1 3LE , United Kingdom

Catalytic C-H bond functionalisation, generally used for the synthesis of fine chemicals [1], has been applied to organometallic luminophores and photochromic systems. Cyclometallated Ir(III) complexes of (hetero)arylpyridines are strongly phosphorescent at room temperature and chemical modification of the cyclometallated ligand enables tuning of the emitting properties. Therefore, a straightforward and selective method for the functionalization of Ir complexes is highly desirable. In this contribution, we present the first example of palladium catalyzed C-H bond activation/arylation of the metallated thiophenes of fac-Ir(N^C3'-thpy)3 (1) with aryl bromides. This method allows the access to new families of Ir(III) complexes, a substantial modulation of their emissive properties being achieved [2].

Furthermore, we report the palladium-catalysed direct regioselective functionalization of DTE (DiThienylEthene) derivatives (2) with (hetero)aryl bromides, giving rise to the formation of new photochromic compounds with either two different or two identical aryl groups. This method which tolerates several functional groups would be useful for the elaboration of photochromic metal complexes [3]. We also demonstrate that Pd-direct coupling of heteroarenes with 1,2-dichlorohexafluorocyclopentene allows to prepare in only one step a wide range of di(aryl)perfluorocyclopentenes. This new route, which avoids the use of highly toxic and volatile octafluorocyclopentene, offers a fast and direct access to symmetrical and unsymmetrical DAE derivatives containing various heterocycles (thiophenes, thiazoles or furans). [1] D. Alberico, M.E. Scott, M. Lautens, Chem. Rev. 2007, 107,174; F. Poznan, J. Roger, H. Doucet, ChemSusChem. 2008,1, 404; J. Roger, F. Poznan, H. Doucet, Green Chem. 2009,11, 425. [2] K. Beydoun, M. Zaarour, J. A. G. Williams, H. Doucet, V. Guerchais, Chem. Commun. 2012, 48, 1260. [3] K. Beydoun, J. Boixel, V. Guerchais, H. Doucet, Catal. Sci. Technol. 2012, 2, 1242. [4] K. Beydoun, J. Boixel, H. Le Bozec, V. Guerchais, H. Doucet, Chem. Commun. 2012, 48, 11951.

O 9

Synthesis of new I r complexes with (P,N) ligands

B raulio A randa,a S.A Moyab, Muriel Escadeillas,c Julien Boixel,c Loïc Toupet,d Pedro Aguir re,a Véronique Guerchais,c Hubert L e Bozec,c

a Facultad de Ciencías Químicas y Farmacéuticas-Universidad de Chile, Santiago, Chile.

bUniversidad de Santiago de Chile, Facultad de Químicas y Biología, Departamento de Ciencias de los Materiales.

c Sciences Chimiques de Rennes UMR 6226 CNRS-Université de Rennes 1 Campus de Beaulieu 35042 Rennes Cedex, F rance

d Institut de Physique de Rennes UMR 6251 CNRS-Université de Rennes 1 Campus de Beaulieu 35042 Rennes Cedex, F rance

Iridium complexes containing phenylated bipyridine ligands have been studied previously in the field of luminescence, showing interesting properties [1]. On the other hand, Ruthenium complexes containing phosphor-nitrogen (PN) ligands have been developed for homogeneous catalysis, showing interesting applications in reactions like hydrogen transfer in imines and ketones[2] On other hand, palladium complexes with PN ligands have been reported in carbonylation reactions with high activities [3]. It is interesting to study the effects of such ligands in luminescent properties, as iridium complexes containing these ligands, such type of studies has not been yet informed Two new complexes, of formula [Ir(Py-NH-PPh2)(MePhPy)2]PF6 (Py = pyridine) and [Ir(Pyr-NH-PPh2)(MePhPy)2]PF6 (Pyr = pyrimidine), were synthesized using reported techniques [1,3], characterized using NMR (1H and 31P), and the corresponding crystalline structures were obtained (fig.1). UV-Vis absorption and emission studies were carried, showing for both complexes two peaks, corresponding to a Ligand-to-Metal Transition Charge and Ligand-to-Ligand Transition Charge, respectively.

Fig.1 Crystalline structures for [Ir(Py-NH-PPh2)(MePhPy)2]PF6 and [Ir(Pyr-NH-

PPh2)(MePhPy)2]PF6. The authors acknowledge the financial support of FONDECYT-Chile (No. 120149 and 1120685). LIA-MIF Project No 836, Chile, France and ECOS-CONICYT No. C07E. G. A. thanks CONICYT for doctoral fellowship B. Aranda (No. 21110568). References: 1. Lepeltier, M.; Lee, T.K-M.; Lo, K. K-W.; Toupet, L.; Le Bozec, H.; Guerchais, V. Eur. J. Inorg. Chem. 2005, 110 2. Zuñiga, C.; Moya, S.A.; Fuentealba, M.; Aranda, B.; Aguirre, P. Inorg. Chem. Comm. 2011, 964. 3. Aguirre, P.; Lagos, C., Moya, S.A., Zúñiga, C., Vera-Oyarce, C., Sola, E., Peris, G., Bayón, J.C., Dalton Trans. 2007, 5419.

O 10 Synthesis and character ization of new M O Fs:

F rom ligand design to porous mater ial topology and chirality

Nathalie Audebrand, 1 F lorian Moreau, 1 Julien Robin 1, Cyril Poriel 2 and Carmelo Prestipino 1

1 Team Solid State Chemistry and Materials Sciences, 2 Team Condensed Mater and Electroactive Systems,

Institute of Chemical Sciences of Rennes - UMR 6226 CNRS, University of Rennes 1, F rance

Metal-Organic Frameworks (MOFs) have become during the past decade one of the most promising classes of synthetic compounds. These materials have potential applications in various fields, from gas storage purification and separation, heterogeneous catalysis or even controlled drug delivery.[1] Their properties mainly rely on the framework design which can be controlled by making a judicious choice of the organic and inorganic parts. Last years we focused our efforts on the synthesis and use of original tetracarboxylate ligands: three 3D ligands exhibiting a tetraphenylmethane core with a tetrahedral geometry and three 2D ligands based on a spirobifluorene (SBF) core with a “square planar” geometry. Furthermore, SBF-based compounds have been mainly used for organic electronics[2], chiral recognition, or asymmetric catalysis[3] until now. Otherwise, it is possible to introduce functional characteristic to these materials. In our work MOFs are functionalized by the introduction of chirality[4] for enantioselective heterogeneous catalysis, which has not been extensively studied to date. We synthesized three new optically pure large spacers containing two or four carboxylate functions based on fluroenyl core which is until now very few used[5] in MOFs design: chiral (S)-2-methylbutyl chains and carboxylic/benzoic/isophthalic functions were grafted on a fluorene core. The reactivity of these ligands towards metal and rare earth salts (ZnII, CuII, CdII, YIII, LaIII) has been studied under various solvothermal conditions. As a result, new families of MOFs were synthesized. Their crystal structures, determined from X-ray diffraction data, show various topologies and interpenetration degrees with sometimes good stability and high potential porosity up to 60% of the cell volume. The modulation of the size of the ligand and the number and position (para/meta) of the carboxyalate functions allows sometimes controlling interpenetration, dimensionality networks and then porosity of the MOFs. In order to control activation of the MOFs, for further potential applications, their thermal behaviours have also been studied by in situ X-ray powder diffraction. In this communication, crystal structures, in situ reactivity, porosity, gas sorption properties, luminescence of the materials as well as catalytic performances for chiral ones will be compared and discussed. References [1] (a) Chem. Rev. (2012) Special issue, vol. 112. (b) “Metal-Organic Frameworks: Design and Applications” ed. L.R. MacGillivray, John Wiley & Sons, Inc., 2010. (c) “Metal-Organic Frameworks: Applications from Catalysis to Gas Storage” ed. D. Farrusseng, Wiley-VCH Verlag GmbH & Co., 2011. (d) F. Moreau, N. Audebrand, C. Poriel, V. Moizan-Baslé, J. Ouvry, J. Mater. Chem. (2011) 21, 18715. [2] T. P.I Saragi, T. Spehr, A. Siebert, T. Fuhrmann-Lieker, J. Salbeck, Chem. Rev. (2007) 107, 1011. [3] J.-H. Xie, Q.-L. Zhou, Acc. Chem. Res. (2008) 41, 581. [4] M. Yoon et. al., Chem. Rev. (2012) 112, 1196. [5] (a) S. Su et. al., CrystEngComm (2011) 13, 2935. (b) J.-P. Ma et. al., Chem. Comm. (2012) 48, 2946.

O 11 Analysis of magnetic properties of organo-inorganic mater ials based

on V O and VPO lattices

M . Saldías a,b, W . Cañónb,c, V . Paredes-García b,d, A .Vega b,d, E . L e Fur e,f, D . Venegas-Yazigi b,g, E . Spodine b,c.

aFacultad de Ciencias Físicas y Matemáticas, U. de Chile, Santiago, Chile. b CEDENNA, Santiago, Chile.

c Facultad de Ciencias Químicas y Farmacéuticas, U. de Chile, Santiago, Chile. d Universidad Andres Bello, Departamento de Ciencias Químicas, Santiago, Chile. eEcole Nationale Superieure de Chimie de Rennes, Rennes, UMR 6226, France. fUniversité de Bretagne, France. g Facultad de Química y Biología,

U. de Santiago de Chile, USACH, Santiago, Chile. The design and synthesis of hybrid materials derived from oxometallic inorganic lattices has focused the attention on materials science due to the possibility of changing the physicochemical properties of the inorganic lattice by the functionalization with both, coordination complexes and/or organic molecules. The VVO and VIVPO lattices can be modified from a magnetic point of view by the functionalization with paramagnetic coordination compounds, such as MnII (3d5) and CuII (3d9) complexes. This work presents the structural and magnetic study of two organo-inorganic materials {(Mn(bipy)}[{VO2(bipy)}(VO3)(V2O6)] (1) and [{Cu(phen)}2(VO)3(PO4)2(HPO4)2]·2H2O (2). Analytical models and DFT calculations allowed to obtain the value of the coupling constant J for (1). The analytical model of a tetranuclear coupled system was used to fit the magnetic data of (2). The obtained values for J1 = -3,5, J2= -47,2, J3= -3,5 and J4=-92 cm-1 give evidence of the antiferromagnetic behavior. The interaction between Cu···Cu (J2) and V···V (J4) are more antiferromagnetic than the mixed interactions. Coupling between ions of equal nature (Cu···Cu and V···V) is favored by the symmetry of the magnetic orbitals. (Figure).

Figure. Exchange pathways for[{Cu(phen)}2(VO)3(PO4)2(HPO4)2]·2H2O (2) Reference. M. Saldias, V. Paredes-Garcia, A. Vega, W. Cañon-Mancisidor, E. Le Fur, D. Venegas-Yazigi, E. Spodine. Polyhedron 41 (2012) 120–126. *This work has been supported by ECOS-CONICYT (Action C08E02).This research has been performed as part of the Chilean-French “Joint Laboratory for Inorganic Functional Materials “ (LIAMIF); CNRS 836.

O 12 Novel transition-metal phosphite compounds with structure related to

yavapaiite: crystal structures and magnetic properties of A I[M II I(HPO3)2] (A= K , N H4, Rb and M=V , Fe)

Farida Hamchaoui a, Véronique A lonzo b, c, Diego Venegas-Yazigi d, Houria

Rebbah a and E ric L e Fur b, c

aLaboratoire des Sciences des Matériaux, Faculté de Chimie, Université des Sciences et de la

Technologie Houari Boumediène, BP 32 El-Alia, 16111 Bab-Ezzouar, Alger, Algeria, bSciences Chimiques de Rennes, UMR6226, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, Avenue du Général Leclerc, CS 50837, 35708 Rennes Cedex 7, F rance, cUniversité Européenne de Bretagne, and

dFacultad de Quimia y Biologia, Universitad de Santiago de Chile, USACH , Casilla, 40 Correo 33, Santiago, Chile.

Since the discovery of the microporous crystalline aluminophosphates in 1980s [1], considerable efforts have been directed towards the synthesis of new open-framework transition metal phosphates due to their rich structural chemistry and potential applications in catalysis, biology, optical and electromagnetic functions [2]. To date, phosphites with transition-metal elements have not been studied widely when compared with the related phosphates which inspired us to synthesize novel phosphite structures incorporating metallic magnetic cations belonging to the first series of the transition elements, particularly in the presence of a second metal atom or of the ammonium ion. With the aim of searching novel transition metal phosphites, we conducted our study on the hydrothermal synthesis in alkali metal – vanadium / iron – phosphite systems. Our efforts have yielded to a novel transition metal phosphites series of isostructural compounds AI[MIII(HPO3)2], ( A=K, NH4, Rb and M=V, Fe). The layered structures of the compounds will be compared to that of the yavapaiite aluns type [3] and to their magnetic properties [4] taking into account the triangular lattice formed by the transition elements. References [1] S.T. Wilson, B.M. Lok, C.A. Messina, T.R. Cannan, E.M. Flanigen, J. Am. Chem. Soc. 104

(1982) 1146. [2] A.K. Cheetham, G. Férey, T. Loiseau, Angew. Chem., Int. Ed. Engl. 38 (1999) 3268. [3] E. J.Graeber, A. Rosenzweig, Am. Mineral. 56 (1971) 1917. [4] H. Serrano-Gonzalez, S.T. Bramwell, K.D.M. Harris, B.M. Kariuki, L. Nixon, I.P. Parkin, C.

Ritter, Phys. Rev. B 59 (1999) 14451. This research has been performed as part of the Chilean-French “Joint Laboratory for Inorganic Functional Materials (LIAMIF).

POSTERS

P 1 Modulating the luminescence of an iridium(I I I) complex incorporating

a di(2-picolyl)anilino-appended bipyridine ligand by Zn2+ cations*

Juan C . A raya,a Juana Gajardo,a Sergio A . Moya,a Pedro Aguir re,b Loïc Toupet,c J. A . Gareth Williams,d Muriel Escadeillas,e Hubert L e Bozec e and Véronique

Guerchais e

a Universidad de Santiago de Chile, Facultad de Química y Biología, Avda. Libertador Bernardo

O’Higgins 3363, Santiago de Chile, Chile b Universidad de Chile, Facultad de Ciencias Química y Farmacéuticas, Casilla 233, Santiago de Chile,

Chile c UMR 6626 (Groupe Matière Condensée) CNRS-Université de Rennes 1, Campus de Beaulieu, 35042

Rennes, F rance d Department of Chemistry, University of Durham, Durham, DH1 3LE , U .K .

e UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes, F rance

Cyclometallated iridium(III) complexes are well known for their rich photochemical and photophysical properties. Among them, cationic N^N-diimine complexes [Ir(N^C-ppy)2(N^N)]+ (where Hppy is 2-phenylpyridine and N^N represents a diimine such as bpy or phen) are particularly attractive. They are readily synthesized, and the facile functionalization of diimine ligands provides access to diverse emissive states, allowing fine-tuning of the optical properties of the complexes. With our continuous interest in the design of phosphorescent Ir(III) complexes, we turned our attention to cationic bipyridine complexes incorporating a styryl group substituted with a di(2-picolyl)amino (DPA) group. In this communication, we report the synthesis, characterization, and photophysical properties of the Ir complex [Ir(N^C-4-Me-ppy)2(N^N-bpy-CH=CH-C6H4-DPA)][PF6] 1 and the changes of its optical properties upon binding of Ni2+, Zn2+, and Cd2+. Binding of Zn2+ gives a unique response, including a significant emission wavelength shift and change in the luminescence lifetime [1].

[1] J.C. Araya, J. Gajardo, S. A. Moya, P. Aguirre, L. Toupet, J. A. G. Williams, M. Escadeillas, H. Le Bozec, V. Guerchais, New. J. Chem., 2010, 34, 21-24. *This work has been supported by ECOS-CONICYT (Action CO7E02).This research has been performed as part of the Chilean-French “Joint Laboratory for Inorganic Functional Materials “ (LIAMIF).

P 2 Caracterización estructural y magnética de nanoespinelas tipo

Nix M3-x O4 (M=Mn, Fe; 0.5<x<2.5) sintetizados por el método sol-gel.

Christian C ruzata)*, O ctavio Peñaa), Yanko Morenob).

a)Institut des Sciences Chimiques, UMR-CNRS 6226, Université de Rennes 1, 35042 Rennes, F rance. b)Depto. Qca. Analítica e Inorgánica, Fac. Cs. Químicas,Universidad de Concepción, Chile .

[email protected] ; [email protected] ; [email protected]. Los óxidos metálicos tienen un gran atractivo para los científicos en aplicaciones biológicas y médicas, en especial en el área del nanomagnetismo1. Los óxidos nanoparticulados son muy investigados por sus nuevas aplicaciones como liberadores de drogas, nanobiosensores y como fluido magnético en hipertermia2 (MFH), el cual se presenta como tratamiento alternativo para combatir el cáncer. En este trabajo se sintetizaron nanoespinelas del tipo NixM3-xO4 (M=Mn, Fe; 0.5<x<2.5) por método Sol-Gel3 para el uso en hipertermia. Se analizaron las muestras por SEM, FESEM, rayos-X de polvo y susceptibilidad magnética. Los análisis elementales a través de SEM-EDX mostraron que todos los compuestos tienen la estequiometría buscada. Los análisis de FESEM indican que es posible cambiar el hábito cristalino de la muestra realizando un trabajo post-sintético. A través de los rayos-X de polvo se determinó el tamaño cristalino promedio utilizando la fórmula de Scherrer y los parámetros de red mediante FullProf suite, vía método de Rietveld. Las medidas de tamaño promedio de las nanopartículas están entre 5 nm y 35 nm. Se realizaron medidas de susceptibilidad magnética para determinar la temperatura de bloqueo de las nanopartículas. La gran mayoría de los compuestos presenta irreversibilidad magnética; en algunos casos a temperatura ambiente.

Fig.1 Micrografías electrónicas de barrido de nanoespinelas del tipo NixM3-xO4 (M=Mn, Fe; 0.5<x<2.5) a) después de la síntesis sol-gel, b) y c) después de realizar el trabajo post-sintético. Agradecimientos: Esta investigación ha sido realizada en el marco del Laboratorio Internacional Asociado Franco-Chileno, LIA MIF 836. C. Cruzat agradece a CONICYT, por financiamiento de BECACHILE, al UMR—CNRS 6226, y al Centro de Microscopía de la Universidad de Rennes1 (www.cmeba. univ-rennes1.fr). Referencias 1.- Cruzat C., Peña O., Díaz J., Cárdenas G., Meléndrez M. Colloid & Polymer Science. 2011, 289, 21. 2.- Horsman M.R., Overgaard J., Clinical Oncology. 2007, 19(6), 418. 3.- Xu J., Yang H., Fu W., et al. Journal of Magnetism and Magnetic Materials. 2007, 309(2), 307.




P 3 Chiral M O Fs from new fluorene-based ligands

for enantioselective catalysis and separation

Julien Robin 1, Nathalie Audebrand, Cyril Poriel 2 and Carmelo Prestipino 1

1 Team Solid State Chemistry and Materials Sciences, 2 Team Condensed Mater and Electroactive Systems,

Institute of Chemical Sciences of Rennes - UMR 6226 CNRS, University of Rennes 1, F rance

Metal-Organic Frameworks (MOFs) have many applications such as gas storage, separation and heterogeneous catalysis1. Our group is focused on the design of original ligands2 and more recently on chiral ligands in order to obtain MOFs for enantioselective catalysis, which has not been extensively studied to date. Our strategy involves the use of an optically pure fluorene based ligand only reported in a few instances as organic linker in MOFs.3 The first step consists to introduce the chirality through the incoporation of optically pure alkyl chains on the methylene bridge of the fluroenyl core. Four original ligands (L1-L4) with different size, different linkers and different connectivities have been synthesized. The reactivity of these new linkers towards metal salts (Zn, Cu, Cd, Y, La …) has been studied under various solvothermal conditions. New MOFs with various topologies have been prepared and their crystal structures have been determined from single-crystal diffraction data. The modulation of the size and of the connectivity allows controlling interpenetration, dimensionality networks and then porosity of the MOFs. For instance for Cu-based MOFs, with dicarboxylate ligand L1, a 2D framework composed of parallel grids is obtained with a potential porosity of 5% (Figure 1). With a larger ligand, containing an additional phenyl group (L2), grids are interpenetrated leading to a 3D framework with a potential porosity of 30% (Figure 1).

F igure 1 : Impact of the size of the dicarboxylate ligand

on the topology of the MOFs.

F igure 2 : Influence of the ligand connectivity (here tetracarboxylate) on the

topology.

To avoid interpenetration, the connectivity of the ligand has been increased (L3) by adding two more carboxylate functions. Then, the resulting 3D framework is non-interpenetrated (Figure 2) with increased potential porosity of 60%. Reactivity of the MOFs is currently studied with X-ray powder diffraction (Laboratory and synchrotron data) to understand the activation processes. Furthermore, catalytic tests are in progress with a benzaldehyde cyanosillylation reaction. References 1 a) G. Férey, Chem. Soc. Rev., (2008), 37, 191. b) D. Farrusseng, Wiley-VCH Verlag GmbH & Co., Metal-Organic Frameworks: Applications from Catalysis to Gas Storage (2011). 2. F. Moreau, N. Audebrand, C. Poriel, V. Moizan-Baslé, J. Ouvry, J. Mater. Chem., (2011), 21, 18715. 3 a) H. D. Guo, X. M. Guo, S. R. Batten,J. F. Song, S. Y. Song, S. Dang, G. L. Zheng, J. K. Tang, H. J. Zhang, Cryst. Growth Des., (2009), 9, 1394; b) N. G. Pschirer,D. M. Ciurtin, M. D. Smith, U. H. F. Bunz, H. C. zur Loye, Angew. Chem. Int. Ed. (2002), 41, 583.

P 4 New hybrid materials based on metal clusters

Antoine Demont†, Nathalie Audebrand†, Stéphane Cordier†, Yuri Mironov‡,

Nikolaï Naumov‡

† Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes I, Avenue du Général Leclerc, 35042 Rennes Cedex F rance, ‡Nikolaev Insitute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Prosp., 630090 Novosibirsk, Russia

Porous luminescent frameworks are a promising class of materials with a wide array of potential applications, such as molecular recognition, non-linear optics or specific radiation detection [1]. Octahedral metallic rhenium cluster cores have been shown to exhibit both the chemical versatility [2] and properties [3] that make them attractive building blocks for the generation of such solids. The [Re6S8(OH)6]4- cluster unit, displaying luminescent properties in the solid state is highly soluble in water, wherein it easily reacts with organic bases such as pyridine derivates to undergo substitution of hydroxyl groups. New materials arising from this interesting reactivity have been synthesized in aqueous solutions, and their crystal structures have been determined from single-crystal X-ray diffraction data. Some of our recent results are presented here, showing the richness of architectures that are accessible via multiple substitutions on the cluster core by distinct ligands. Moreover owing to the six positions where ligand substitutions for hydroxyl groups can occur on the [Re6S8(OH)6]4- cluster unit, stereoisomery relationships (figure 1) are found. For instance the isomery of the bi-substituted cluster unit (cis or trans) depicted in figure 1 allows to stabilize dramatically distinct frameworks.

F igure 1: a),b) double substitution of hydroxyl groups by pyrazine on the

[Re6S8(OH)6]4- cluster a) cis stereoisomer, b) trans stereoisomer and c),d) their respective crystal structures in the solid state.

[1] M. D. Allendorf, C.A. Bauer, R. K. Bhakta, R. J. T. Houk, Chem. Soc. Rev., 2009, 38, 1330–1352 [2] Cordier, S.; Dorson, F.; Grasset, F.; Molard, Y.; Fabre, B.; Haneda, H.; Sasaki, T.; Mortier, M.; Ababou-Girard, S.; Perrin, C.; Journal of Cluster Science (2009), 20(1), 9-21 [3] Yoshimura, Takashi; Ishizaka, Shoji; Sasaki, Yoichi; Kim, Haeng-Boo; Kitamura, Noboru; Naumov, Nikolai G.; Sokolov, Maxim N.; Fedorov, Vladimir E.; Chemistry Letters (1999), (10), 1121-1122 ; Arratia-Perez, Ramiro; Hernandez-Acevedo, Lucia; Journal of Chemical Physics (1999), 111(1), 168-172 ; Gray, Thomas G.; Rudzinski, Christina M.; Nocera, Daniel G.; Holm, R. H.; Inorganic Chemistry (1999), 38(26), 5932-5933; Yoshimura, Takashi; Ishizaka, Shoji; Umakoshi, Keisuke; Sasaki, Yoichi; Kim, Haeng-Boo; Kitamura, Noboru; Chemistry Letters (1999), (7), 697-698.

P 5 Magnetic and catalytic properties of (La, Y , E r)Co0.5Mn0.5O3

perovskites*

C laudia M Camposa,b , G ina Pecchia, Eduardo J. Delgadoa, O ctavio Peñab

a: Facultad Ciencias Químicas, Universidad Concepción, Casilla 160-C , Concepción, Chile. b: Sciences Chimiques de Rennes, UMR 6226, CNRS, Université de Rennes 1, Rennes, F rance.

RECo0.5Mn0.5O3 materials (RE: La, Y, Er) prepared by a citrate and calcined at 700, 850 and 950°C show the perovskite structure at temperatures as low as 700°C, much lower than the temperatures required by ceramic methods of solid-state synthesis. Materials prepared by this technique show adequate specific surface when calcined at 700°C. Catalytic activity was evaluated using the total combustion of methane as reaction test. The catalytic activity, higher at lower calcination temperatures, can be related to the presence of the perovskite structure, an adequate surface area and the reducibility of the material. Catalytic activity is progressively lost due to a sintering process which occurs when the material is calcined at higher temperatures, as observed by SEM techniques [1].

[1] G. Pecchi, C.M. Campos, O.Peña. Catalysis Today, 172 (2011) 111-117. *This work has been supported by Fondecyt 1090018.This research has been performed as part of the Chilean-French “Joint Laboratory for Inorganic Functional Materials “ (LIAMIF).

700°C

850°C

950°C

P 6 E ffect of particle size of Cu-Gd and Cu-Eu M O F catalysts in olefin

oxidation

Patricio Cancino,a,c Pedro Aguir rea, Verónica Paredes-Garcíab,c, E ric L e Furd,e, Evgenia Spodinea,c

aUniversidad de Chile, Facultad de Ciencias Químicas y Farmacéuticas (Chile). E-mail:

[email protected] bUniversidad Andres Bello, Departamento de Ciencias Químicas (Chile).

cCEDENNA (Chile) d ENSCR, CNRS, UMR 6226, Rennes, (F rance). e Université Européenne de Bretagne, (F rance).

In the field of catalysis the superficial area is most important for a good performance of the catalyst, and the possibility to obtain compounds with nanometric particle size has shown an increase in the conversion of many systems, as compared to the results obtained with the bulk catalyst[1]. Metal organic frameworks (MOFs) present structural versatility and porous structures which make them interesting for the use in heterogeneous catalysis. This work analyzes the effect of particle size of [Cu3Ln2(oda)6(H2O)6]∙12H2O (Ln: Gd or Eu) (oda: oxydiacetate) MOFs as heterogeneous catalysts on the catalytic properties for styrene and cyclohexene oxidation. The synthesis of the heterometallic Cu-Gd and Cu-Eu MOFs was made following the experimental procedure described in [2] and through which it was possible to obtain a particle size of of 20 μm for Cu-Gd and 18 μm for Cu-Eu. When the experimental conditions are modified by the introduction in the reacting media, of the surfactant hexadecylamine, the particle size decrease to 10 μm in Cu-Gd* and 8 μm in Cu-Eu* MOFs. These heterometallic MOFs were used as catalysts in olefin oxidation, considering styrene and cyclohexene as substrates. The products for styrene oxidation were 1-phenylacetaldehyde, styrene oxide and benzaldehyde. The selectivity was modified when the particle size became smaller, showing a decrease of the yield of styrene oxide from 41% to 28%. Contrary, the selectivity showed an increase in styrene oxide from 33% to 38% when Cu-Eu and Cu-Eu* are used, respectively. The catalytic results for the oxidation reaction of cyclohexene do not show important variations with the particle size, giving an average conversion of 34 %, with 2-cyclohexen-1-one as the main product.

[1] D. Jiang, T. Mallat, F. Krumeich, A. Baiker, Catal Comm, 2011, 12, 602-605. [2] R. Baggio, M.T. Garland, Y. Moreno, O. Peña, M. Perec, E. Spodine. J.Chem.Soc, Dalton Trans, 2000, 2061-2066 Acknowledgements The authors thank Financiamiento Basal, FB0807 project, and PC thanks CONICYT for a doctoral scholarship 21110228 “Programa de Formación de Capital Humano Avanzado”. This work was done under the LIA-MIF CNRS 836 Collaborative Program.

Fig 1. Structure for [Cu3Ln2(oda)6(H2O)6]•12H2O

Fig 2. Conversion and chemoselectivity for 24h of reaction.


P 7 Catalytic properties of supported polyoxometalates on natural zeolites

M . Gutiér rez a,b, D . A ltbir b,c, E . Spodine b,d, D . Venegas-Yazigi a,b

a Facultad de Química y Biología, Universidad de Santiago de Chile, USACH;

b CEDENNA; c Facultad de Ciencia, Universidad de Santiago de Chile, USACH

dFacultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile. During the last decade, a large part of the studies in nanoscience and nanotechnology have been focused on the preparation and characterization of nanostructured materials. An important group of nanostructured materials present catalytic properties. Studies to develop new types of nanostructured catalysts to obtain products with high yield and high purity are a central issue in materials science. Polyoxometalates (POMs) are a family of polyanions, which present a great versatility as building blocks for the design of multifunctional materials. They are also very versatile from an electronic point of view, due to their wide variety of electronic states, which makes them very attractive for redox reactions, and optic and magnetic applications. Polyoxomolybdates and polyoxovanadates can be obtained as molecular polianions, with different nuclearities which vary from a few centres to more than 150 metallic centres (1). The use of these POMs as catalysts is reflected in the large number of articles and patents published over the years. The development of ecological systems based on hydrogen peroxide and molecular oxygen in the catalytic oxidation of organic substrates by incorporating the use of POMs has been previously reported (2). Zeolites are natural species based on alumino-silicates. These species can be modified in order to change their superficial charge, and therefore different species can be sorbed. Thus the functionalization of zeolites with POMs makes them interesting as heterogeneous catalysts. In this work the catalytic properties, of the [V18O42(H2O)]12- polyanion supported on natural zeolites, on the oxidation reaction of olefins is presented (3). References 1.- Müller,A., Sessoli, R., Krickemeyer, E., Bögge, H., Meyer, J., Gatteschi, D., Pardi, L., Westphal, J., Hovemeier, K., Rohlfing, R., Döring, J., Hellweg, F., Beugholt, C., Schmidtmann, M., 1997, Inorganic Chemistry, 36, 5239-5250. 2.- Keita, B., Nadjo, L., 2007, Journal of Molecular Catalysis A: Chemical, 262, 2–6. 3.- Leus, K., Vandichel, M., Liu, Y., Muylaert, I., Musschoot, J., Pyl, S., Vrielinck, H., Callens, F., Marin, G.B., Detavernier, C., Wiper, P.V., Khimyak, Y.Z., Waroquier, M., Van Speybroeck, V., Van Der Voort, P., 2012, Journal of Catalysis, 285, 196–207. Acknowledgements Authors acknowledge partial financial support from FONDECYT 1120004 and Financiamiento Basal (CEDENNA) FB0807 projects. Authors also thank the International Collaborative Program LIA-MIF 836.

P 8 Estudio de la reacción de 2,2,2-trialcoxi-4,5-dimetil-1,3,2-

dioxafosfolano frente a fer roceno-carboxaldehido.

Guillermo Ahumadaa, David Carrilloa, Carolina Manzura, Jean-René Hamonb.

aLaboratorio de Química Inorgánica, Instituto de Química, Pontificia Universidad Católica de Valparaíso, Campus Curauma, Avenida Universidad 330, Valparaíso, Chile Fax: +56 3222749 32.

b UMR 6226 Institut des Sciences Chimiques de Rennes, CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France Fax: 02 23235637.

Email: [email protected]

Es bien sabido que aldehídos aromáticos reaccionan con el aducto 2,2,2-trialcoxi-4,5-dimetil-1,3,2-dioxofosfolano, formando una estructura cíclica saturada (oxifosforano) que, de acuerdo a las condiciones de reacción, deriva en α,β-dihidroxicetonas o en la forma enólica de 2,4-butanodionas1. En este trabajo se muestran los productos de reacción entre este aducto y el ferroceno-carboxaldehído los que fueron identificados como 1-ferrocenil-1,2-propanodiona (figura 1), 3-hidroxi-4-metoxi-butanodiona (figura 2) y 4-ferrocenil-3-metil-3-buten-2-ona (figura 3). Los productos fueron caracterizados por FT-IR, 1H-, 13C- RMN y difracción de rayos X de monocristal.

(Figura1) (Figura 2) (Figura 3) Referencias: 1. a) Fausto Ramírez, A. V. Patwardhan, N. Ramanathan, N. B. Desai, C. V. Greco, S. R. Heller. J. Am. Chem. Soc., 1965, 87, 543; b) D. Pawlica, M. Marszalck, G. Mynarczuk, L. Sieron, J. Filmes, New J. Chem. 2004, 28, 1615. Los autores agradecen al proyecto FONDECYT Nº 1090310, al Laboratorio Internacional Asociado (LIA MIF N° 836), y a la Vicerrectoría de Investigación y Estudios Avanzados de la P. Universidad Católica de Valparaíso. G.A. agradece a CONICYT por beca doctoral otorgada.


P 9 Magnetismo en compuestos de coordinacion basados en Cu(hfac)2

R . A r rue-Muñoz,a,b) Y . Moreno,a) A . Lara, a) O . Pena,b) T . Rousnel,b).J. Y . Pivanc)

a)Facultad de Ciencias Químicas, Universidad de Concepción, Chile

b) Equipe de Chimie Solied et Materiaux Université de Rennes 1, F rance c)Ecole National Superieure du Chimie Rennes, F rance1

El presente trabajo está compuesto por la síntesis en solución los compuestos Cu(acac)2 (acac=acetilacetonato), Cu(hfac)2H2O (hfac=1,1,1,5,5,5-hexafluoro-2,5-pentanodiona), y Cu(hfac)2(Tz)2 (Tz=tiazol), su caracterización estructural y el estudio de sus propiedades magnéticas. Se caracterizaron los compuestos mediante espectroscopía IR y Difracción de Rayos X en monocristal y se determinó el momento magnético efectivo y se estudió la presencia de fenómenos magnéticos cooperativos utilizando un magnetómetro SQUID. Los compuestos Cu(acac)2 y Cu(hfac)2(Tz)2 presentan valores de momento magnético efectivo del orden de 1.80μB, sin embargo Cu(hfac)2 se obtuvo un valor ligeramente más alto (1.92μB) el que está en relación con la menor distancia entre los centros paramagnéticos dando lugar a una interacción más favorable. Se propone una nueva ruta de síntesis para Cu(hfac)2 la que un rendimiento muy superior a la reportada por Bertrand y Kaplan1. Se propone para trabajos futuros el uso de ligandos heterociclos radicales difuncionalizados con el objeto de producir sistemas 1D, 2D o 3D donde los centros paramagnéticos estén más cerca unos de otros favoreciendo la interacción magnética.

Fig.1 Inverso de susceptibilidad magnética versus temperatura para los compuestos sintetizados.

Fig.2 Estructuras de los compuestos sintetizados resueltas por DRX en monocristal.

Referencias 1. Bertrand, J. A.; Kaplan, R. I., A Study of Bis(hexafluoroacetylacetonato) copper(II). Inorganic Chemistry 1966, 5, (3), 489-491. Agradecimientos: Proyecto CNRS-CONICYT n° EDC 24746, Rennes Metropole para movilidad doctoral. Beca Doctoral CONICYT n° 21100076. Universidad de Concepción, DIUC 211.021.031-1.0 This research has been performed as part of the Chilean-French “Joint Laboratory for Inorganic Functional Materials (LIAMIF).

P 10 Structural and magnetic character ization of polymetallic compounds

containing carboxylate as bridging ligand

Veronica Paredes-García* a,b, Bianca Baldob, Ignacio Rojasb, Rosa Madridb, Andres Vega a,b, Diego Venegas-Yazigib,c, Evgenia Spodineb,d

a Universidad Andres Bello, Departamento de Ciencias Químicas, Santiago, Chile.

b Centro para el Desarrollo de la Nanociencia y Nanotecnología, CED ENNA, Chile. c Facultad de Química y Biología, Universidad de Santiago de Chile, USACH , Chile.

d Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Chile. Polymetallic compounds containing carboxylate as bridging ligand are attractive not only by the different coordination modes of the carboxylate group but also because the caboxylate groups allow the magnetic exchange between the metal ions. The structural diversity can be achieved using different synthetic strategies, and depending on the experimental conditions and the precursors used, it is possible to obtain, molecular structures, mono-, bi- or three-dimensional compounds. In this work, we are informing the structural and magnetic characterization of three compounds which contains carboxylate groups in the structure. One of them, based on the acetate group [Cu2(Ac)4(CONH2)2] (1), presents the copper(II) ions pentacoordinated to five oxygen atoms. Four oxygen atoms of the acetate bridges coordinate in a syn-syn conformation, generating a paddlewheel type structure, while the fifth oxygen corresponds to an acetamido group. The Cu…Cu distance is 2.610 Å. The compounds (2) and (3) are based on the formate ligand which generates three dimensional networks. In compound (2) the formate anion coordinates in an anti-anti fashion generating parallelepipeds which produce the 412·63 topology of [Fe(HCOO)3]∞·(HCOOH)6 (2). In this structure, the iron ion Fe (III) presents a highly regular octahedral coordination, in which the six positions are occupied by oxygen atoms belonging to the formate ligand. The Fe…Fe distance is 6.042Å. The compound (3), displays triangular Mn3 building blocks, in which the metal centers are bonded by formate ligands in a syn-anti mode (Mn-Mn 5.697(1) Å). The coordination sphere of manganese(II) is completed by six oxygen atoms from six formate ligands, giving an octahedral geometry with a 33·56 topology . All compounds are characterized for presenting antiferromagnetic interactions between the metal ions and details of the structural and magnetic behavior of each compound will be discussed in this work. Acknowledgments The authors acknowledge FONDECYT 1090477 and Financiamiento Basal CEDENNA FB0807 projects for financial support. The authors also acknowledge the LIA-MIF 836 International collaborative project.

P 11 Síntesis de un ligando bipiridínico conteniendo un fragmento

diarileteno*

Matias V idal,a Sergio A . Moya,a Pedro Aguir re,b Hubert L e Bozec c and Véronique Guerchais c

a Universidad de Santiago de Chile, Facultad de Química y Biología, Avda. Libertador Bernardo

O’Higgins 3363, Santiago de Chile, Chile b Universidad de Chile, Facultad de Ciencias Química y Farmacéuticas, Casilla 233, Santiago de Chile,

Chile e UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes, F rance

Se ha puesto gran atención en el potencial que pudiesen tener ciertos materiales moleculares en fotónica y en dispositivos emisores de luz [1]. Adicionalmente, un creciente interés ha apuntado al desarrollo de numerosos cromóforos con respuestas ópticas no lineales (ONL), principalmente dipolos monodimensionales [2]. La síntesis y caracterización de un fragmento diarileteno conteniendo un grupo aldehído fue lograda con éxito. Este grupo funcional, mediante un acoplamiento Wittig-Horner, permite el acoplamiento de bifosfonato de bipiridina formando un ligando polipiridínico con actividad fotoluminiscente de posible interés en el ámbito de la óptica no-lineal. El siguiente diagrama muestra la reacción entre las dos especies mencionadas en solución de THF y en presencia de una base fuerte que inicia la reacción:

SS

MeO N

N

SS

OMe

F

F

FFF

F

FFF

F FF

Referencias 1.- O. Maury, J. Guégan, T. Renouard, A. Hilton, P. Dupau, N. Sandon, L. Toupet, H. Le Bozec., New J. Chem, 2001, 25, 1553. . 2.- K. Senéchal, O. Maury, H. Le Bozec, I. Ledoux, J. Zyss., J. Am. Chem. Soc. 2002, 124, 4560. Este trabajo ha sido financiado por ECOS-CONICYT (Proyecto CO7E02). Esta investigación ha sido realizada en el marco del Proyecto chileno-francés "Laboratorio de Materiales Inorganicos Funcionales" (LIAMIF). SAM agradece a Fondecyt (Proyecto1120685). MV agradece a Conicyt por las becas de Doctorado y apoyo de Tesis.

P 12 E fecto de la sustitución catiónica y de la formación de espacios vacíos

en tioespinelas CuMx T i2-xS4 (M = Fe, Mn)

P. Barahona a)*, A . Galdámez b), V . Manríquez b), O . Peña c).

a)Facultad de Ciencias Básicas. Universidad Católica del Maule. Talca. Chile b)Facultad de Ciencias. Universidad de Chile. Santiago. Chile.

c)Sciences Chimiques de Rennes, UMR 626, Université de Rennes 1, Rennes, F rance Las tioespinelas con formula genérica AB2S4 son conocidas por mostrar una variedad de interesantes propiedades físicas. Estas propiedades pueden cambiar, por una parte, con la sustitución. Por ejemplo, CuTi2S4 posee estructura espinela y muestra propiedades metálicas sin anomalías magnéticas. Cuando en este compuesto se sustituye parte de los cationes titanio por cromo, sucesivos cambios magnéticos ocurren con el incremento de cromo, desde vidrios de espín a un régimen ferrimagnético 1,2. Por otra parte, las propiedades físicas pueden cambiar cuando se realizan cambios en los estados de oxidación de los átomos de los compuestos. Esto último se puede lograr al realizar extracciones de uno de los cationes de la espinela. En este trabajo presentamos la síntesis y propiedades magnéticas de los compuestos obtenidos por sustitución catiónica en CuTi2S4 con Mn y Fe para obtener CuMnxTi2-xS4 y CuFexTi2-xS4 respectivamente. Además se realizan la síntesis de los compuestos deficientes en cobre de los compuestos con I2/CH3CN. Con el propósito de determinar el orden magnético se realizaron ciclos ZFC/FC a bajo campo de los compuestos CuMnxTi2-xS4 y CuFexTi2-xS4. La Figura 1 muestra un comportamiento similar para CuMnTiS4 y CuFeTiS4 con una transición magnética antiferromagnética bajo los 10 K. A pesar de las interacciones antiferromagnéticas observadas, caracterizadas por el valor negativo de θ (-250 K), el compuesto CuFeTiS4 muestra una no despreciable componente ferromagnética, como queda en evidencia en el ciclo de magntezación M(H) como función del campo (Figura 2).

0 10 20 30 40 500.00

0.01

0.02

0.03

0.04

0.05

0.06

Temperature (K)

ZFC CuMnTiS4 FC CuMnTiS4 ZFC CuFeTiS4 FC CuFeTiS4

-50 -25 0 25 50-0,15

-0,10

-0,05

0,00

0,05

0,10

0,15

-3 0 3

-0,01

0,00

0,01

Mag

netiz

ació

n (

B)

Campo Magnético (KOe)

CuFeTiS4

Fig.1Magnetización ZFC/FC Fig.2 Magnetización a T =2K

Referencias 1 F. Kariya, S. Ebisu and S. Nagata, J. Solid. State Chem. 2009, 183, 608 2 P. Barahona, A. Galdámez, V. Manríquez and O. Peña, J. Alloys and Cmpds., 2009, 480, 291 (2009). Agradecimientos: FONDECYT N° 1110161, LIA-MIF N° 836, ECOS/CONICYT C09E01.

P 13 D F T studies of the magnetic properties of the tridimensional network

[Fe(H C O2)3]n∙nHCO2

Walter Cañón-Mancisidor*a,b, Veronica Paredes-García b,c, Ignacio Rojas c, Rosa Madrid c, Andres Vega b,c, Evgenia Spodine a,b , Diego Venegas-Yazigi b,d.

a Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Chile.

b Centro para el Desarrollo de la Nanociencia y Nanotecnología, CEDENNA, Chile. c Universidad Andrés Bello, Departamento de Ciencias Químicas, Santiago, Chile.

d Facultad de Química y Biología, Universidad de Santiago de Chile, USACH , Chile. Polymetallic compounds containing carboxylates as bridging ligands are attractive from a magneto-structural point of view, mainly due to the possibility of obtaining a broad diversity of products with new and sophisticated architectures based on molecular, mono-, bi- or three-dimensional frameworks.[1-2] A new three-dimensional porous metal organic framework (MOF) based on iron(III) and formate ligands, [Fe(HCO2)3]n∙nHCO2H (1) was obtained using solvothermal conditions. The tridimensional structure crystallizes in the trigonal space group R3c and is formed by highly regular octahedral Fe(OHCO)6 units. The system presents an antiferromagnetic behaviour in the 296 to 20 K range. The fit of the experimental data between room temperature and 50 K, using the high temperature series model (HTS model) permits to estimate a J value of -1.01 cm-1. In order to study the magnetic properties, DFT calculations were performed on a dinuclear fragment of the studied compound. The dinuclear model is representative of all super-exchange interactions present in the 3D lattice. The calculated exchange interaction is antiferromagnetic and relatively weak with a value of Jcalc = -2.38 cm-1, which is in agreement with the expected magnetic properties of formate bridged systems in an anti-anti coordination mode. References [1] D. Piñero, P. Baran, R. Boca, R. Herchel, M. Klein, R.G. Raptis, F. Renz and Y. Sanakis, Inorg. Chem. 2007, 46, 10981. [2] V. Paredes-Garcia, A. Vega, M.A. Novak, M.G.F. Vaz, D.A. Souza, D. Venegas-Yazigi and E. Spodine, Inorg. Chem. 2009, 48, 4737. Acknowledgments The authors acknowledge FONDECYT 1090477 and Financiamiento Basal CEDENNA FB0807 projects for financial support. The authors also acknowledge the LIA-MIF 836 International collaborative project. Powered@NL HPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02), Center for Mathematical Modeling CMM, Universidad de Chile.

P 14 Theoretical studies of the magnetic properties of extended V(I I I) and

Fe(I I I) phosphite isostructural systems

Walter Cañón-Mancisidor*a,b , E ric L e-Furc,d , Farida Hamchaouie , Houria Rebbahe , Evgenia Spodinea,b , Diego Venegas-Yazigi*b,f

a Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Chile.

b Centro para el Desarrollo de la Nanociencia y Nanotecnología, CEDENNA, Chile. c Sciences Chimiques de Rennes, UMR6226, Ecole Nationale Supérieure de Chimie de Rennes, CNRS,

F rance. d Université Europeénne de Bretagne, F rance.

e Laboratoire des Sciences des Matériaux, Université de Sciences et de la Technologie Houari Boumediène, Algeria.

f F acultad de Química y Biología, Universidad de Santiago de Chile, USACH , Chile

Considerable efforts have been directed towards the synthesis of new open-framework transition metal phosphates due to their rich structural chemistry and potential applications in catalysis, biology, optical and electro-magnetic functions [1]. In this context, the phosphite group, HPO3

2-, which is closely related to the phosphate group, can also be incorporated as a basic building unit to obtain new structures with interesting magnetic properties. Since a better understanding of the magnetic properties of polymetallic systems requires a description of their electronic structure, theoretical calculations using Density Functional Theory (DFT) are used as a powerful tool for the description of the different exchange pathways present in the structure of these extended systems [2]. In this work, the theoretical study of the magnetic properties of four layered transition metal phosphites A[M(HPO3)2], where A = K+, Rb+ and M = FeIII, VIII is presented. The magnetic properties of these systems were calculated using a trinuclear fragment of the original structure, which forms an equilateral triangle. On the other hand, the exchange interaction between layers mediated by the alkaline cations is also studied. References [1] A.K. Cheetham, G. Ferey, T. Loiseau, Angew. Chem. Int. Ed. 1999, 38, 3268. [2] E. Ruiz, J. Cano, P. Alemany, S. Alvarez, M. Verdaguer, Phys. Rev. B. 2000, 61, 54. Acknowledgments The authors acknowledge Financiamiento Basal CEDENNA FB0807 projects for financial support. This work was supported by the Algerian - French program CMEP-PHC Tassili 10 MDU 819. The authors also acknowledge the LIA-MIF 836 International collaborative project. Powered@NL HPC: This research was partially supported by the supercomputing infrastructure of the NLHPC (ECM-02), Center for Mathematical Modeling CMM, Universidad de Chile.

P 15 Luminescent materials: Applications in solid-state lighting

devices and solar cells

Jaime L lanos and Darío Espinoza

Universidad Católica del Norte, Departamento de Química, Avda. Angamos 0610, Antofagasta, Chile. (e_mail: [email protected])

About 70% of the electrical power consumed in our modern society is produced from fossil fuels (coal, natural gas, oil), and it is well-known that the decreased availability of these resources, together with the detrimental long-term effects of emissions of CO2 and other greenhouse gases into the atmosphere, has lead to a double-sided crisis that faces humanity with the necessity of developing new alternatives to produce energy from a variety of resources in a cleaner and more efficient way. The design of new materials that can be used in the development of alternative sources of energy or more efficient materials that would reduce the global demand for electricity in widespread applications in industry, buildings, and transportation is thus one of the most important challenges for solid-state chemist and materials scientist. In this regard, the development of new systems for solid-state lighting (SSL) that could help in dropping substantially the electricity consumption or the development of new sources of energy has been of high interest. Between the new energy sources proposed, one the most import and promising is the direct conversion of solar energy to electricity by photovoltaic cells. At present the photovoltaic area is predominantly based on crystalline and polycrystalline silicon. Nevertheless, in the last decade dye sensitized solar cells (DSSC) have appeared as a low cost alternative. An important role in these areas has been played by the chemistry of the rare-earth elements. Nowadays, the lanthanide elements have been considered the “jewels of the functional materials” and specifically, the interest in this chemistry has been focused on the preparation of new luminescent or energy converting materials, known generically as inorganic phosphors. Our interest has been centered in the search for new photo-luminescent materials to be used as efficient red and green-emitting phosphors for SSL devices based on InGaN LEDs, and their application as down-conversion materials in dye sensitized solar cells. Our interest is to determine how these inorganic phosphors can help in improving the light-harvesting process increasing the photocurrent in these solar cells. Acknowledgments: This work was supported by Fondecyt (1090327).

P 16 Síntesis y caracter ización de nuevos comple jos con potenciales propiedades O N L , que contienen bases de Schiff asimétr icas

sustituidas con grupos aceptores

J. C isternaa, D . Car rilloa, C . Manzura, J.-R .Hamonb

aLaboratorio de química inorgánica, Instituto de química, Pontificia Universidad Católica de Valparaíso, Campus Curauma, Avenida universidad 330, Valparaíso, Chile.

E- mail: [email protected], [email protected] b UMR SciencesChimiques de Rennes, CNRS-Université de Rennes 1, Campus de Beaulieu, 35042

Rennes Cedex, France. El interés por diseñar y construir nuevos materiales con propiedades Ópticas No-Lineales de Segundo Orden (ONL-2), ha sido un desafío en la última década, gracias a sus potenciales aplicaciones en tecnología fotónica y optoelectrónica [1]. En los últimos años se ha logrado sintetizar y caracterizar complejos metálicos asimétricos de bases de Schiff (BS), funcionalizados con grupos aceptores y dadores de electrones, para generar un alto momento dipolar, que es un requisito fundamental en cromóforos ONL-2[1-2]. En este trabajo se presentan nuevos compuestos de coordinación de Ni(II) y Cu(II), a partir de un ligando “half-unit”[3] via condensación de aldehídos aromáticos con diferentes sustituyentes electro-aceptores, tales como NO2 y F (ver Esquema). Estos compuestos han sido caracterizados mediante técnicas espectroscópicas convencionales (RMN 1H y FT-IR). Se espera determinar sus estructuras cristalinas y moleculares mediante difracción de rayos-X de mono-cristal. Referencias: 1 A. Trujillo, M. Fuentealba, D. Carrillo, C. Manzur, I. Ledoux-Rak, J.-R. , J.-Y. Saillard, inorg. Chem. 2010, 49, 2750. 2 A. Trujillo, S. Sinbandhit, L. Toupet, D. Carrillo, C. Manzur, J.-R. Hamon, J. Inorg. Organomet. Polym. 2008, 18, 81. Referencias: 1. A. Trujillo, M. Fuentealba, D. Carrillo, C. Manzur, I. Ledoux-Rak, J.-R. , J.-Y. Saillard, inorg. Chem. 2010, 49, 2750. 2. A. Trujillo, S. Sinbandhit, L. Toupet, D. Carrillo, C. Manzur, J.-R. Hamon, J. Inorg. Organomet. Polym. 2008, 18, 81. 3. M. Fuentealba, A. Trujillo, J.-R. Hamon, D. Carrillo, C. Manzur, J. Mol. Struct. 2008, 881, 76. Agradecimientos: Los autores agradecen a FONDECYT (Proyecto N° 1090310) y al Laboratorio Internacional Asociado LIA MIF N° 836. J. C. agradece a CONICYT por su beca de doctorado.

Esquema de síntesis de complejos asimétricos de bases de Schiff (BS).

P 17 Synthesis, structural characterization and study of the electronic

properties organic and organometallic bichalcones

Fernanda O cayoa, Vania A rtigasa, Judith A . K . Howardb, Jean-Yves Saillardc, Samia K ahlalc, Mauricio Fuentealbab,d, Carlos A . Escobara and A lexander

T ruj illoa

aUniversidad Andres Bello, Facultad de Ciencias Exactas, Departamento de Ciencias Químicas,

Santiago Chile. bDepartment of Chemistry. Durham University. South Road, Durham. DH1 3LE . UK .

cSciences Chimiques de Rennes UMR 6226 Université de Rennes 1 Campus de Beaulieu. Rennes, F rance dPontificia Universidad Católica de Valparaíso, Avenida . Universidad 330, Curauma, Valparaıso, Chile The Chalcones (1,3-diaryl-2-propen-1-ones) have been widely used in designing systems that find applications as diverse as multi-sensor[1,2] or new materials[3]. In this work we discuss strategies for preparing synthetic organic bichalconas, from 1,1 ́-diformyl-biphenyl and organometallic from its analogue, 1,1 ́-diformyl-ferrocene. Also presented are the molecular structures of 3,3 ́-di-(3 - (2- hydroxyphenyl)-3-oxo-1-propenyl)-biphenyl (1) and 1,1 ́-di-(3 - (2 -hydroxyphenyl)-3-oxo-1-propenyl)-ferrocene (2), and its analogs, which have been characterized using X-ray diffraction . The characterization of the absorption spectra of the compound (2) in five different solvents suggests that this compound exhibits nonlinear optical properties [4]. Will also be discussed in this work the electronic properties of analogous compounds of (1) and (2). Also, by means DFT calculations was performed for describe its electronic structure.

Acknowledgments: The authors thank FONDECYT Project N°1080147 and LIA MIF 836. Reference: 1.-Liu, M.; Wilairat, P.; Go, M. L. Journal of Medicinal Chemistry 2001, 44, 4443-4452. 2.-Avaux-Nicot, B.; Maynadi, J.; Lavabre, D.; Lepetit, C.; Donnadieu, B. Eur.J.Inorg.Chem. 2005, 2005, 2493-2505. 3.-Shettigar, S.; Chandrasekharan, K.; Umesh, G.; Sarojini, B. K.; Narayana, B. Polymer 2006, 47, 3565- 3567. 4- Di Bella, S. Chem.Soc.Rev. 2001, 30, 355-366.

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