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Séparés par des virgules

Groupe Mercier

(Nicolas Mercier, (Pr. responsable), Marie-Claire Dul (MCF) , Magali Allain (I.E.))

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

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 (2, 3).

Visuel matériaux luminescents

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

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).

Visuel ligands organiques portant des charges positive

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)

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).

Visuel des paramètres clés causant les propriétés photochromiques des hybrides méthylviologène-chlorobismuthate

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)
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) 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)

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 at 298K, which was a record in the field of hybrid ferroelectrics (4-1).

Visuel des pérovskites hybrides ferroélectriques

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)
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)

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.

Visuel des perovskites hybrides commutables NLO

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)
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)

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)).

Visuel des perovskites hybrides semi-conducteurs

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)
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)
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)
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)