Laboratory MOLTECH-Anjou
 

Présentation of the CIMI (Chimie Inorganique, Matériaux et Interfaces)

    Responsible : Narcis AVARVARI

     

    Permanent people

    Magali Allain (IE University)

    Narcis Avarvari (DR2 CNRS)

    Patrick Batail (DR1 CNRS)

    Thomas Cauchy (MC)

    Marie-Claire Dul (MC)

    Abdelkrim El-Ghayoury (MC - HDR)

    Michel Giffard (MC)

    Nicolas Mercier (PR)

    Cécile Mézière (IE CNRS)

    Non-Permanent people

    Antonin Leblanc (PhD student)

    Maxime Leroux (PhD student)

    Kévin Martin (PhD student)

    Nabil Mroweh (PhD student)

    Cristina Oliveras (PhD student)

    Oleh Stetsiuk (PhD student)

     

     

     

     

     


     

     

    Abstract of the CIMI group activities

     

    The research activities of the CIMI team are related to several topics developed by the three independent groups, yet having as common points the utilization of crystallography (single crystal and powder) as an analysis tool of diverse materials, as well as the close collaboration with physicists of the condensed matter. The choice of the molecular precursors is essential for the preparation of the molecular or hybrid materials, as well as for the targeted properties. The contribution of the organic and inorganic synthesis, solid state chemistry, coordination chemistry, crystal engineering, and theoretical chemistry, both to molecular and periodical level, is very important.

     

     

    Group Batail
    (Patrick Batail, Thomas Cauchy, Cécile Mézière)

     

     

     

     

    IFunctional molecular systems engineering, metals and molecular superconductors to molecular motors: what determines the structure, which determines the property. Strongly correlated systems and photo-induced phenomena.

     

     

     

     

     

     

    Group Mercier
    (Nicolas MercierLeader), Marie-Claire Dul (MCF) , Magali Allain (Engineer), Maxime Leroux (PHD 2014-..), Antonin Leblanc (PHD 2016-..))

     

    Organic-Inorganic materials : from Hybrid Perovskites to Complexes and Porous Coordination Polymers


     

    1- Bi complexes : high luminescence QY and MCL.


    We recently discovered a new family of highly luminescent materials based on bipyridine-N-oxide derivatives and Bi3+ or Pb2+ cations, with solid state Quantum Yields (QY) up to 85%. The origin of the photoluminescence is of phosphorescence type (1-1). Interestingly, these compounds can exhibit Mechanochromic Luminescence (MCL) properties : under grinding the emission color is changing while the reversibility of the process can be achieved by heating or fuming. These compounds are the first bismuth based MCL complexes (1-2, 1-3).


    1-1 Aggregation Induced Phosphorescent N-Oxyde-2,2’-Bipyridine Bismuth Complexes and Polymorphism-Dependent Emission
    O. Toma, N. Mercier,* M. Allain, A. Forni, F. Meinardi, C. Botta
    Dalton Trans., 2015, 44, 14589-14593

    1-2 Bismuth based Coordination Polymers with Highly Efficient Aggregation Induced Phosphorescence and Reversible Mechanochromic Luminescence
    O. Toma, M. Allain, F. Meinardi, A. Forni,* C. Botta,* N. Mercier,*
    Angew. Chemie Int. Ed., 2016, 55, 7998-8002

    1-3  Process-Dependent Reversible Mechanochromic Luminescence of Bismuth based Polymorphs
    O. Toma, N. Mercier,*C. Botta*
    J. Mater. Chem. C., 2016, 4, 5940-5944.

     

    2- PCPs based on viologen-carboxylate ligands.


    While the main strategy to increase the H2 or CO2 uptake has been to introduce coordinatively unsaturated metal centers, we have recently proposed to use organic ligands bearing positive charges. The PCPs which are aimed are based on “bipyridinium-carboxylate” ligands.Not only ensuring the cationic nature of organic linkers, such moieties have capabilities to make donor-acceptor interactions with guest molecules (sensor applications). The first results show that some materials exhibiting different photo- or thermochromic properties depending on the adsorbed molecule (2-1).

     

    2-1 Photo-, Thermo-chromic and Adsorption Properties of Porous Coordination Polymers based on Bipyridinium Carboxylate Ligands
    O. Toma, N. Mercier,* M. Allain, A. Kassiba, J. P. Bellat, G. Weber, I. Bezverkhyy.
    Inorg. Chem., 2015, 54, 8923-8930 (WS 07/2016: 3 citations)

     

     

    3- Photochromic viologen based hybrids

    The key parameters causing the photochromic properties of methylviologen chlorobismuthate hybrids have been explored. Several derivatives have been synthesized to see the effects of the anionic oligomer size, of the substituting of Bi by Sb, Cl by Br or MV2+ by other viologens (V), on the photo-induced charge transfer process (3-1, 3-2). All these results have been summarized in an invited article of Microreview type in Eur. J. of Inorg. Chem. (3-3).

     

    3-1 Photochromism, Electrical Properties and Structural Investigations of a Series of Hydrated Methylviologen HaloBismuthate Hybrids:….
    N. Leblanc, W. Bi, N. Mercier,* P. Auban-Senzier and C. Pasquier
    Inorg. Chem. 2010, 49, 5824-5833  (WS 07/2016: 36 citations)


    3-2 Stable Photo-Induced Separated Charge State in Viologen halometallates: Some Key Parameters.
    N. Leblanc, M. Allain, N. Mercier*, L. Sanguinet
    Cryst. Growth Des. 2011, 11, 2064-2069 (WS 07/2016: 40 citations)


    3-3  The Templating Effect and Photochemistry of Viologens in Halometalate Hybrid Crystals
    N. Mercier*
    Eur. J. Inorg. Chem. 2013, 19–31 – microreview –(WS 07/2016 : 15 citations)

     


    4- Ferroelectric hybrid perovskites

     


    A new family of hybrid ferroelectrics with the formulation of (MV)[M(III)X5] (MV2+ methylviologen, M= Bi, Sb; X= Cl, Br, I) has been discovered (4-1, 4-2). In particular, the mixed halide hybrid (MV)[BiI3Cl2] is very interesting : its polarization curve shows an ideal hysteresis and its saturated polarization is of 15 mC.cm-2  at 298K, which was a record in the field of hybrid ferroelectrics (4-1).

     


    4-1 Large Spontaneous Polarization and Clear Hysteresis Loop of a Room Temperature Hybrid Ferroelectric Based on Mixed Halide [BiI3Cl2] Polar Chains and Methylviologen Dication.
    N. Leblanc, N. Mercier,* L. Zorina, S. Simonov, P. Auban-Senzier, C. Pasquier*
    J. Am. Chem. Soc. 2011, 133, 14924  (WS 07/2016: 38 citations)


    4-2 Thermally induced Bi(III) lone pair stereoactivity: Ferroelectric Phase Transition and Semiconducting Properties of (MV)BiBr5 (MV= methylviologen)
    W. Bi, N. Leblanc, N. Mercier,* P. Auban-Senzier, C. Pasquier                
    Chem Mater 2009, 21, 4099-4101 (WS 07/2016: 47 citations)

     

    5- NLO switchable hybrid perovskites

     

    The association of polarizable and acentric (ns2 lone pair stereoactivty) iodometallate anions to a disulfide derivative which can possess two chiral conformations, has lead to materials with switchable SHG properties along with the temperature (5-1, 5-2). The presence of a hysteresis in the SHG= f(T) curve shows that the change 1 (SHG active)) / 0 (SHG inactive) can be achieved by an external stimulus such as the pressure or irradiation.

     

    5-1 A switchable NLO organic-inorganic compound based on conformationally chiral disulfide molecules and Bi(III)I5 iodobismuthate networks.
    W.Bi, N. Louvain, N. Mercier,* J. Luc, I. Rau, F. Kajzar, B. Sahraoui         
    Adv. Mater. 2008, 20, 1013   (WS 07/2016: 111 citations)


    5-2 Conglomerate to True Racemate Reversible Solid State Transition in Crystals of an Organic Disulfide Based Iodoplombate
    N. Mercier,*A.-L. Barres, M. Giffard, I. Rau, F. Kajzar, B. Sahraoui
    Angew. Chemie, Int. Ed. 2006, 45, 2100-2103  (WS 07/2016: 60 citations)

     

    6- Semiconducting hybrid perovskites

     

     

    In the field of hybrid perovskites ((R-NH3)2M(II)I4 (R= alkyl, M=Sn, Pb)), we have proposed several strategies to increase mobilities of these materials (p- materials with FET mobilities up to 0.5 cm2 V-1s-1). The main strategy to reduce the VB-CB gap was to design materials with limited distorsions of inorganic layers, by selecting suitable organic cations able to make hydrogen and halogen bonding (6-2, 6-3). All these results have been summarized in an invited article (Highlight type-CrysEngComm (6-1)).

     

    6-1 Structural Diversity and Retro-Crystal Engineering Analysis of Iodometalate hybrids
    N. Mercier,* N. Louvain, W. Bi           
    CrystEngComm 2009, 11, 720-734 – Highlight article (WS 07/2016: 81 citations)


    6-2- Reduced Band Gap Hybrid Perovskites Resulting from Combined Hydrogen and Halogen Bonding at the Organic-Inorganic Interface
    S. Sourisseau, N. Louvain, W. Bi, N. Mercier,* D. Rondeau, F. Boucher, JY Buzaré, C. Legein
    Chem. Mater. 2007, 19, 600 (WS 07/2016: 86 citations)


    6-3 Unique hydrogen bonding correlates with a reduced band gap and phase transition in the hybrid perovskites (HO-(CH2)2-NH3)2PbX4 (X = I, Br)
    N. Mercier,* S. Poiroux, A. Riou, P. Batail
    Inorg. Chem. , 2004, 43, 8361 (WS 07/2016: 66 citations)


    6-4 Effect of mono- versus di-ammonium cation of 2,2’-bithiophene derivatives on the structure of organic-inorganic hybrid materials based on iodo metallates
    X.-H. Zhu, N. Mercier*, P. Frère, P. Blanchard, J. Roncali, M. Allain, C. Pasquier, A. Riou
    Inorg. Chem. 2003, 42, 5330 (WS 07/2016 : 87 citations)

    Top

     

     

     

    Group Avarvari

     

    a. Chirality and tetrathiafulvalenes (Narcis Avarvari, Thomas Cauchy)

     

    A recent direction in the field of the multifunctional molecular materials is represented by the chiral conductors, for which one of the major interests is the electrical magneto-chiral anisotropy effect. This phenomenon, evidenced in particularly for the chiral carbon nanotubes, explains the interplay between chirality and conductivity and should be observed in the transport properties under magnetic field. However, the combination chirality – electroactivity is interesting for more than one reason: modulation of the chiroptical properties with the oxidation state of the TTF; electroactive assemblies (gels, nanofibers, etc.) by supramolecular chirality; influence of the structural disorder on the conducting properties; electroactive ligands for the enantioselective catalysis.

     

    In this respect we are currently developing several families of chiral donors: TTF-oxazolines, TTF-sulfoxides, methylated BEDT-TTF, C3 symmetric tris(TTFs). The collaboration with physicists of the condensed matter for the study of the transport properties is very active.

    Publications :


    1) “Tetrathiafulvalene based phosphino-oxazolines: a new family of redox active chiral ligands” C. Réthoré, M. Fourmigué, N. Avarvari, Chem. Commun. 2004, 1384–1385.
    2) “Chiral Molecular Metals: Syntheses, Structures and Properties of the AsF6− Salts of Racemic (+/−), (R)- and (S)-Tetrathiafulvalene-Oxazoline Derivatives”, C. Réthoré, N. Avarvari, E. Canadell, P. Auban-Senzier, M. Fourmigué, J. Am. Chem. Soc. 2005, 127, 5748–5749. >
    3) "Chiral tetrathiafulvalene based phosphine- and thiomethyl-oxazoline ligands. Evaluation in palladium catalysed asymmetric allylic alkylation", C. Réthoré, I. Suisse, F. Agbossou-Niedercorn, E. Guillamón, R. Llusar, M. Fourmigué, N. Avarvari, Tetrahedron 2006, 62, 11942–11947. >
    4) ″Chemo- and Enantioselective Sulfoxidation of Bis(ethylenedithio)-Tetrathiafulvalene (BEDT-TTF) into Chiral BEDT-TTF-Sulfoxide″, M. Chas, M. Lemarié, M. Gulea, N. Avarvari, Chem. Commun. 2008, 220–222.
    5) “Chiralité et électroactivité : des conducteurs moléculaires à la catalyse asymétrique. Précurseurs électroactifs chiraux basés sur le motif tétrathiafulvalène-oxazoline (TTF-OX)”, N. Avarvari, Actualité Chimique (account article), 2009, 333, 18–24.
    6) “Supramolecular Electroactive Organogel and Conducting Nanofibers with C3-Symmetrical Architectures”, I. Danila, F. Riobé, J. Puigmartí-Luis, Á. Pérez del Pino, J. D. Wallis, D. B. Amabilino, N. Avarvari, J. Mater. Chem. 2009, 19, 4495–4504.
    7) “Strategies towards chiral molecular conductors”, N. Avarvari, J. D. Wallis, J. Mater. Chem. (feature article) 2009, 19, 4061–4076.
    8) “C2-Symmetric chiral tetrathiafulvalene-bis(oxazolines) (TTF-BOX): new precursors for organic materials and electroactive metal complexes”, F. Riobé, N. Avarvari, Chem. Commun. 2009, 3753–3755. >
    9) “Order versus Disorder in Chiral Tetrathiafulvalene–Oxazolines Radical Cation Salts: Structural, Theoretical Investigations and Physical Properties”, A. M. Madalan, C. Réthoré, M. Fourmigué, E. Canadell, E. B. Lopes, M. Almeida, P. Auban-Senzier, N. Avarvari, Chem. Eur. J. 2010, 16, 528–537.
    10) “Electroactive oxazoline ligands”, F. Riobé, N. Avarvari, Coord. Chem. Rev. 2010, 254, 1523–1533.

     

    b. Electroactive ligands (Narcis Avarvari, Abdelkrim El-Ghayoury)

     

     

    The covalent association of TTF redox active units and diverse ligands is interesting for several reasons.First, it allows for the preparation of electroactive coordination complexes with possible electronic communication between the metal and the TTF fragment. In this case, the redox properties of TTF be influenced by the coordinated metal, and, reciprocally, the electron density on the metal can vary with the oxidation state of TTF. Another aspect is related to the possible template role of the metal when assembling two or more TTF units in its coordination sphere. A third important point is the access to multifunctional molecular materials.

     

    Publications:

    1) “Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts”, D. Lorcy, N. Bellec, M. Fourmigué, N. Avarvari, Coord. Chem. Rev. (review article) 2009, 253, 1398–1438.

     

    c. Rigid dimers, intramolecular mixed valence (Narcis Avarvari, Ion Danila)

     

     

    The direct covalent connectivity, or through spacers, of two or more TTF units represent a valuable strategy to access multi-redox systems in which the degree of intramolecular electronic communication, through bond or through space, is of paramount importance in order to reach mixed valence states. In this context we are developing a family of rigid bis(TTFs) containing heteroatom bridges.

     

    1) “1,4-Dihydro-1,4-diphosphinine Fused with Two Tetrathiafulvalenes”, N. Avarvari, M. Fourmigué, Chem. Commun. 2004, 2794–2795.


    2) "Intramolecular Mixed Valence State Through Silicon or Germanium Double Bridges in Rigid Bis(Tetrathiafulvalenes)", F. Biaso, M. Geoffroy, E. Canadell, P. Auban-Senzier, E. Levillain, M. Fourmigué, N. Avarvari, Chem. Eur. J. 2007, 13, 5394–5400.


    3) “Rigid Bis(Tetrathiafulvalenes) Doubly Bridged by Phosphino Groups and Derivatives: Synthesis and Intramolecular Mixed Valence State”, I. Danila, F. Biaso, H. Sidorenkova, M. Geoffroy, M. Fourmigué, E. Levillain, N. Avarvari, Organometallics 2009, 28, 3691–3699.

     

    d. Donor-acceptor Systems
    (Narcis Avarvari, Flavia Pop, Thomas Cauchy)

     

     

     

    We have started a systemic investigation on new donor-acceptor derivatives showing an intramolecular charge transfer. This type of compounds are interesting for various fields such as molecular electronic and optoelectronics, solar cells, non linear optics. We are particularly interested by TTF-nitrogen based heterocycles compounds.

     

     

    Publications :

    1) “Mono- and Bis-Tetrathiafulvalene-1,3,5-Triazines as Covalently Linked Donor-Acceptor Systems: Structural, Spectroscopic and Theoretical Investigations”, F. Riobé, P. Grosshans, H. Sidorenkova, M. Geoffroy, N. Avarvari, Chem. Eur. J. 2009, 15, 380–387.

     

     

    e.Extended homo-and hetero-polymetallic coordination networks
    (Narcis Avarvari, Abdelkrim El-Ghayoury, Diana Branzea)

     

    This topic is based on the use of novel bis and tris(phosphonate) ligands in order to built coordination networks by design.

     

    Publications :


    1) “C3 Symmetric Tris(phosphonate)-1,3,5-triazine Ligand: Homopolymetallic Complexes and Its Radical Anion”, C. Maxim, A. Matni, M. Geoffroy, M. Andruh, N. Hearns, R. Clérac, N. Avarvari, New J. Chem.2010, DOI: 10.1039/c0nj00204f

     

     

Top