IPCM

4.Design of nano-capsules : Guest encapsulation, chiral recognition and chemistry in confined environment.

ricci — 2011-11-25T15:05:57Z

I. Nanocapsules and host-guest chemistry.

Rational design of inorganic artificial receptors for host-guest chemistry is an attractive area in contemporary inorganic chemistry. Self-assembly constitute an elegant method for the preparation of elaborate architectures. The use of appropriate inorganic bricks and rationally chosen ligands allows the preparation of appealing metallo-cages that may display potential applications in various fields such as electronic, ion sensing and catalysis. Our group is highly active in this area. Previously we described the first examples of irido-cryptand/cryptates, in which the BF₄- anion is encapsulated through hydrogen bonding. Pursuing our research, we recently reported the rational design of a variety of Co(II) and Cu(II) capsules in which the weakly coordinating anion such as BF₄- or PF₆- play a pivotal role as template, around which, metallic cations and ligands self-assemble. These capsules were obtained in high yields and were fully characterized by X-Ray and solution or solid state NMR.

Figure. Nanocapsules of Co(II) and Cu(II) templated by BF4- anions : ACIE. 2005, 44, 4543. Chem. Eur. J. 2007, 13, 5401. Eur. J. Inorg. Chem, 2009, 29, 4396. Dalton Trans. 2009, 10429.

II-Chiral metallomacrocycles

Half-sandwich complexes with three-legged piano stool geometry with different substituents are archetypal examples of optically active chiral-at-metal center. Such species are ubiquitous in organometallic synthesis and catalysis, however more recently it has become clear that they can be very interesting building blocks for supramolecular chemistry. We reported the synthesis of some Chiral metallo-macrocycles by treating the solvated half-sandwich complexes [(π-arène)M(solvent)₃]²⁺ (π-arène = η-C₆H₆, η-Cp, η-Cp*) with trifunctional ligands (see drawing). These macrocycles are obtained as racemates, through homochiral self-assembly (all metal centers have the same configuration) R_MR_MR_M and S_MS_MS_M with a 1 : 1 ratio of both diastereomers. Resolution of these metallo-macrocycles was achieved using chiral anion auxiliary.

Figure. Chiral metallomacrocycles of rhodium R_RhR_RhR_Rh / S_RhS_RhS_Rh. The S-enantiomer exhibits chiral recognition to Δ-Trisphat. Inorg. Chem. 2004, 43, 6644. Organometallics. 2007, 26, 860.

Our current investigations are devoted to the elaboration of new chiral nanocapsules with large cavities capable to house molecules or even inorganic complexes, with the objective to carry out chemical transformations in a confined environment.

Figure. View of metallomacrocycles with chiral bridging ligands.

3.Organometallic catalysis, resolution of metal complexes via chiral anion recognition.

ricci — 2011-11-25T14:16:21Z

Resolution of a rare binuclear ruthenium compounds via chiral anion recognition
The binuclear ruthenium trans-[bis(Cp*Ru)-carbazolyl][PF₆], has a C₂ symmetry and belongs to compounds with planar chirality (Figure 1).

a) b)

Figure. a) Binuclear ruthenium complex trans-[bis(Cp*Ru)-carbazolyl][PF₆] ; b) Structure of trans-[(Sp,Sp)-bis(Cp*Ru)-carbazolyl][Δ-Trisphat] showing chiral anion recognition. Organometallics 2004, 23, 4338.

The PF_6- anion of the racemic dinuclear ruthenium compound can be replaced by Δ-Trisphat through anion metathesis to give two pair of diastereomers. These diastereomers [trans-[(Sp,Sp)-bis(Cp*Ru)-carbazolyl][Δ-Trisphat] and trans-[(Rp,Rp)-bis(Cp*Ru)-carbazolyl][Δ-Trisphat] can be separated by fractional crystallization. X-ray molecular structure of the trans-[(Sp,Sp)-bis(Cp*Ru)-carbazolyl][Δ-Trisphat] was ascertained by single crystal X-ray diffraction study. The complex crystallizes in the chiral space group P21. The absolute configuration was determined by using the Flack's parameter (x = 0.07). The CD curve of the crystal was recorded and confirmed the configuration obtained from the X-ray study.

Our future objectives is devoted to the use of such chiral complexes as ligands to promote enantioselective catalytic C-C bond formation.

2.Luminescent properties of coordination assemblies with organometallic linkers for optoelectronic applications.

ricci — 2011-11-25T13:21:36Z

I- Coordination chains and polymers Our group has recently designed a new family of organometallic o- and p-quinonoïd complexes of iridium and rhodium. These compounds were used as organometallic-linkers "OM-linkers" to construct a novel class of luminescent coordination assemblies and polymers. Interestingly the chalcogen atoms of the p-quinonoïd complexes (Figure) are highly nucleophilic and hence are able to bind a wide range of transition metal based chromophores such as Cu(I), Ag (I), Ru(II), Pt(II), Rh(III) and Ir(III). Moreover the related o- and p-thioquinonoid OM-linkers (E= S,) were prepared for the first time following an appropriate synthetic procedure. These highly reactive intermediates were metal-stabilized and isolated as "Cp*Ir" complexes.

Figure : Organometallic o- and p-Quinonoïd Complexes : ACIE 2008, 47, 1372.

The dithiobenzoquinone complexes (E=S) are of particular interest since they allowed the preparation of a new family of polypyridyl platinum(II) compounds exhibiting important π–π and Pt(II)•••Pt(II) interactions responsible of thermochromism and photoluminescence properties (Collaboration Prof V. W. W. Yam). These compounds are potentially of great interest as luminescent material devices.

Figure : Photoluminescence and Thermochromism behavior of 1D Pt-chain with p-thioquinonoid OM- Dalton Trans. 2007, 3526.

More recently we were able to isolate the first example of a diselenobenzoquinone (E= Se) as a metal complex. The X-ray molecular structure of this molecule was determined. Furthermore this species exhibited important antitumoral properties comparable to that of cis-platin. This work was heralded the cover of the prestigious journal Angewandte Chemie.

Figure : Molecular structure of the p-diselenobenzoquinone as a metal complex : ACIE 2010, 49, 7530.

II. Chiral octahedral assemblies

Another interesting family of chiral octahedral Ir(III), Rh(III) and Ru(II) was also designed and successfully prepared using the o-quinonoid metal-complexes. The resulting chiral bimetallic assemblies showed interesting photoluminescence properties such as panchromatic absorbers and NIR emissions. These complexes hold promise for applications in the area of optoelectronics and photovolatics.

Figure : Luminescent chiral bimetallic assemblies with o-quinonoid OM-linker (M2 = Ru, Rh, Ir). Organometallics 2009, 28, 397. Inorg. Chem. 2010, 49, 10762.

III-Anion-π interactions in quinonoid OM-linkers.

Furthermore we have recently demonstrated that this kind of quinonoid OM-linkers display important noncovalent interactions with anions despite the fact they are neutral. In fact, the weakly coordinating anion triflate undergoes an anion-π interaction with the Cp*Ir moiety of the neutral quinonoid linker in the organometallic assembly [Cp*Ir(η⁶-C₆H₂O₄)-(BF₂)₂] et l'anion triflate (CF₃SO₃‾) (see Figure). The work has been published in Eur. J. Inorg. Chem. and was featured on the cover of the journal.

Figure.View of the anionic part of the organometallic assembly with atom numbering system. (b) The CF₃SO₃ anion is perfectly located on top of Cp*Ir and lies on the same plane of symmetry as that of [Cp*Ir(η⁶-C₆H₂O₄)-(BF₂)₂]( c ) C---O short contacts are shown by dotted lines.. Eur. J. Inorg. Chem. 2009, 3679.

Our future objectives in this research topic are devoted to the use of the new tetradentate p-quinonoid linkers for the preparation of luminescent chiral networks.

1.Chirality : from molecular complexes to coordination assemblies and material networks.

ricci — 2011-11-25T12:52:31Z

Chirality in Transition metal Chemistry : Molecules, Supramolecular assemblies & Materials.
H. Amouri & M. Gruselle ; Wiley : Chichester, UK., Novembre 2008.

Chirality is an ever-fascinating topic and is a field, which occurs in various subjects of modern chemistry. Our group has an international expertise in this area and this field represents the cornerstone on which our research activities rely upon. Thus we have prepared variety of chiral structures from mononuclear to coordination assemblies including chiral networks. These compounds exhibit interesting properties see below :

I- Chiral quinone methides

Quinone Methides act as important intermediates in organic syntheses as well as in chemical and biological processes, however examples of isolated species are scarce as a result of their high reactivity. We reported the synthesis and reactivity of the first stable iridium and rhodium o-quinone methide complexes. These compounds undergo interesting C-C bond forming reactions with variety of alkenes and alkynes, further they exhibit planar chirality, hence their differentiation and resolution are stimulating and challenging objectives especially in asymmetric C-C coupling reactions.

Figure. Optically pure metal-stabilized quinone methides. Acc. Chem. Res. 2002, 35, 501. Organometallics 2005, 24, 4240.

II- Bimetallic clusters possessing acetylenic ligands.

Alkyne-dicobalt carbonyl complexes display tetrahedral geometry. They are chiral if the four vertices have different functional groups (Figure). Another method to prepare chiral bimetallic cluster consists of introducing a linker between one of the two metallic centers and carbon vertices. In this example the chirality of the complex can be better described as central chirality (Figure). On the other hand if the two metal centers are linked to the methylene groups of the bridging alkyne, the obtained compound will be chiral with C2-symmetry and should display helical chirality. We prepared a chiral binuclear cobalt complexes of the formula [Co₂(CO)₄µ,η²,η²-(-H₂CC≡CCH₂-)(-L-L)₂][Δ-Trisphat]₂ {L-L = dppm, NH(PPh₂)₂}, which represent a rare example of an organometallic compound displaying helicoïdal symmetry (Figure 3). The two diastereomers with (Δ, Δ) et (Λ, Δ) were separated through column chromatography.

a) b)

Enantiomère Λ ou M Enantiomère Δ ou P

Figure. a) Chiral bimetallic cobalt complex with centered chirality. b) Two bladed Chiral bimetallic cobalt complexes with helical chirality (the carbonyl ligands were removed for clarity). Chirality in Transion Metal Chemistry : Molecules, supramolecular assemblies and materials Chichester Wiley 2008.

III-Chiral coordination networks (2-3D)

Oxalate ligands (C₂O₄)^2- have been widely used to construct a variety of coordination networks. In this work we describe an enantioselective method to prepare optically active networks of the formula [cation][M1M2(C₂O₄)₃]_n. These chiral networks are obtained upon treatment of the resolved building blocks (Δ)- or (Λ)-[M1(C₂O₄)₃]^n- with inorganic brick M2X₂ (X= monovalent anion) in presence of a cation. The relative configuration of the connected hexacoordinated centres determines the 2D or 3D architecture of the metal-organic framework. A hetero-chiral arrangement [(Δ)-M1(Λ)-M2)] leads to a 2D network. In contrast, a homo-chiral arrangement [(Δ)-M1(Δ)-M2)] leads to a 3D helical organisation of the connected metallic ions.

Figure. Schematic drawing of (Λ) and (Δ) enantiomers of [M1(C₂O₄)₃]^n- metallobricks. Coord. Chem. Rev. 2006, 250, 2491.

Service de mesures magnétiques

ricci — 2011-11-21T13:57:14Z

ce service fait partie de la plate-forme UPMC de mesures physiques à basse température

Contact pour l'IPMC :
Yanling li
UMR 7201 IPCM
Bâtiment F74 4^ème étage
case courrier 42 Bureau 452
4 place Jussieu 75252 Paris cedex 05.
Tel : 01 44 27 30 59 (bureau) ou 01 44 27 58 74 (squid)
Courriel : Yanling Li

Appareils

MPMS-XL7
Mesures de moment magnétique sous champ statique (DC)
Mesures moment magnétique sous champ alternatif (AC)
Champ ultra faible
Contrôle dispositif externe (EDC)
Rotateur horizontal
Transport RSO

MPMS-5S
Mesures de moment magnétique sous champ statique (DC)
Mesures moment magnétique sous champ alternatif (AC)

Localisation des magnétomètres sous sol salle n° 6 Couloir 22-32 INSP(Institut de Nanoscience de Paris), 4 place Jussieu 75252 Paris cedex

Possibilités de mesures :

Champ DC jusqu'à 7 Teslas ; champ AC jusqu'à 3.5 Oe avec fréquence de 0.01 à 1000 Hz
Mesures magnétiques sous irradiation de la lumière blanche avec canne équipée de fibres optiques
Annulation de champ résiduel
Mesures sur monocristaux, poudres, suspensions et liquides

Conditions d'accès : mesures magnétiques sur demande, possibilité de self-service après formation.

Traitements de données : nous élaborons des codes de calcul en MathematicaTM pour des traitements de données spécifiques.

Liens : http://www.qdusa.com/ , Site de la plateforme UPMC (en construction)


Principe de fonctionnement de magnétomètre à SQUID


Exemples d'application dans le domaine de matériaux moléculaires

4. Wheel-shaped and spherical metal oxide-based clusters (in collaboration with A. Müller, Bielefeld University - Germany)

ricci — 2011-11-21T09:41:10Z

Reduced Molybenum-Oxide-Based Core–Shell Hybrids : “Blue” Electrons Are Delocalized on the Shell
A. M. Todea, J. Szakács, S. Konar, H. Bögge, D. C. Crans, T. Glaser, H. Rousselière, R. Thouvenot, P. Gouzerh and A. Müller, Chem. Eur. J., 2011, 17, 6635–6642.

Competition for electrons : In metal-oxide-based core–shell hybrids, in which the core (Keggin ion) as well as the shell (Keplerate cluster) can both easily be reduced, the electrons appear preferably delocalized on the shell.

Unprecedented and Differently Applicable Pentagonal Units in a Dynamic Library : A Keplerate of the Type {(W)W₅}₁₂{Mo₂}₃₀
C. Schäffer, A. Merca, H. Bögge, A. M. Todea, M. L. Kistler, T. Liu, R. Thouvenot, P. Gouzerh, A. Müller, Angew. Chem. Int. Ed., 2009, 149-153.

Magic pentagons : Exploitation of versatile pentagonal units/ligands has previously led to giant molybdenum oxide based curved species, including spherical Keplerates. Similar methodology is now also applicable to the related tungstate scenario (see corresponding basic central pentagonal unit in green).

Vectorial growth/regulations in a {P₈W₄₈}-type polyoxotungstate compartment : trapped unusual molybdenum oxide acts as a handle
F. L. Sousa, H. Bögge, A. Merca, P. Gouzerh, R. Thouvenot, A Müller, Chem. Commun., 2009, 7491-7493.

Reaction of the cyclic {P₈W₄₈} polyoxotungstate host with sodium molybdate in solution in the presence of a reducing agent leads to the formation and stabilization of unprecedented neutral {Mo^V₄O₁₀(H₂O)₃} aggregates with handle function, thereby proving the potential of the present host for performing future interesting studies related to mixed-valence type chemistry under confined conditions.

Plates-forme technique DRX

ricci — 2011-08-30T13:58:50Z

La plate-forme technique DRX de la Fédération FR2769 réalise la caractérisation structurale de composés par diffraction des rayons X sur monocristaux .

La prise en charge d'un échantillon implique :
le choix du cristal et sa préparation puis, si la qualité cristalline est suffisante,
l'acquisition d'un jeu de données de diffraction
la résolution puis l'affinement de la structure cristalline
la mise en forme des résultats.

Nous réalisons également des études en température ou travailler sur détermination de configurations absolues.

Contacts plate-forme DRX pour l'IPCM :
Responsable scientifique : K. Boubekeur (tel. : 01 44 27 30 34)
L-M. Chamoreau (tel. : 01 44 27 30 90)
G. Gontard (tel. : 01 44 27 30 90)
P. Herson (01 44 27 55 28)

Campus Jussieu - Bâtiment F - 4ème étage
pièce 435 ou 446
4 place Jussieu
75252 Paris cedex 5

A -Instrumentation :

Diffractomètre Bruker AXS Kappa-APEX II (année 2010)
système de régulation de température à l'azote liquide Oxford Cryostream Plus : de 80 à 490 K
Source : tube scellé Molybdène + monochromateur TRIUMPH (cristal courbe de graphite)
Géométrie : Kappa
Détecteur : APEX II
Utilisation : Composés inorganiques et organiques

Diffractomètre Bruker AXS QUAZAR (année 2011)
système de régulation de température à l'azote Oxford Cryostream 700 : de 80 à 400 K
Source : microsource Cuivre
Géométrie : Kappa
Détecteur : APEX II
Utilisation : composés organiques, détermination de configuration absolue, mailles élémentaires à grands paramètres

La plate-forme dispose également :
d'une loupe binoculaire (grossissement x50) avec lumière polarisée et caméra vidéo
de la base de données cristallographique Cambridge Structural Database recensant les structures cristallines des composés contenant au moins une liaison C-H

B - Quelques exemples d'études structurales :

	Synthesis and Application in Catalysis of Planar Chiral (η5-cyclohexadienyl)tricarbonylmanganese Based Ligands Rose-Munch, F. ; Cetiner, D. ; Chavarot-Kerlidou, M. ; Rose, E. ; Agbossou-Niedercorn, F. ; Chamoreau, L.-M. ; Gontard, G. Organometallics, 2011, 30(13), 3530-3543
	Dimensionality Switching Through a Thermally Induced Reversible Single-Crystal-to-Single-Crystal Phase Transition in a Cyanide Complex Gheorghe, R. ; Kalisz, M. ; Clerac, R. ; Mathoniere, C. ; Herson, P. ; Li, Y. ; Seuleiman, M. ; Lescouezec, R. ; Lloret, F. ; Julve, M. Inorganic Chemistry , 2010, 49, 11045-11056.
	Regioselective Cobalt-Catalyzed Formation of Bicyclic 3- and 4-Aminopyridines Garcia, P. ; Evanno, Y. ; George, P. ; Sevrin, M. ; Ricci, G. ; Malacria, M. ; Aubert, C. ; Gandon, V. Organic Letters, 2011, 13, 2030–2033
	Insights into the Coordination Chemistry of Phosphonate Derivatives of Heteropolyoxotungstates Villanneau, R. ; Racimor, D. ; Messner-Henning, E. ; Rousseliere, H. ; Picart, S. ; Thouvenot, R. ; Proust, A. Inorganic Chemistry, 2011, 50, 1164-1166.

Plate-forme RMN

ricci — 2011-08-30T07:47:46Z

L'IPCM est l'utilisateur principal de plusieurs spectromètres RMN appartenant à la plate-forme RMN de la Fédération FR2769. Les spectromètres RMN (haute résolution en phase liquide) présentés ci-dessous sont situés dans les locaux de l'IPCM sur le campus de Jussieu.

Ces spectromètres RMN sont des outils d'analyse utilisés quotidiennement par les chercheurs pour le suivi des synthèses, la caractérisation de routine en chimie moléculaire, ou pour réaliser des études RMN plus complexes sur certains produits.

Contacts plate-forme RMN pour l'IPMC :
Elsa Caytan (tel. 01 44 27 59 96)
Geoffrey Gontard (tel 01 44 27 30 90)

RMN Bruker 6OOMHz

Console Avance III
Logiciel d'exploitation : topspin 2.1
Parc de sondes :
- BBFO (sonde directe, ¹H, ¹³C, ³¹P, ¹¹B,… et ¹⁹F, avec accord de sonde automatique + gradients)
- TXI (sonde inverse de 1,7mm, ¹H, ¹³C et ¹⁵N, avec accord de sonde automatique + gradients),
- BBO (sonde directe 10mm, ¹H, ¹³C, ³¹P, ¹¹B,…, avec accord de sonde automatique + gradients), Sonde triple inverse de 5mm (¹H, ³¹P et noyaux bas γ + gradients)
Localisation : bâtiment 31, RdC
Utilisation : expériences de longue durée (utilisation du passeur d'échantillon possible) Sur réservation uniquement. (Contact : Elsa Caytan ou Geoffrey Gontard)
Historique : aimant et console installés en mars 2010

RMN Bruker 4OOMHz :

Console Avance III nanobay
Logiciel d'exploitation : topspin 2.1
Sonde : BBFO (sonde directe, ¹H, ¹³C, ³¹P, ¹¹B,… et ¹⁹F, avec accord de sonde automatique + gradients)
Localisation : bâtiment F, 2^ème étage, pièce 241
Utilisation : libre-service pour des expériences de routine en journée, et expériences longues la nuit grâce au passeur d'échantillons. (contact : Elsa Caytan)
Historique : aimant installé en 2001, sonde acquise en 2007, console installée en 2009

RMN Bruker 3OOMHz :

Console Avance III nanobay
Logiciel d'exploitation : topspin 3.0
Sonde : BBFO (sonde directe, ¹H, ¹³C, ³¹P, ¹¹B,… et ¹⁹F, avec accord de sonde automatique + gradients)
Localisation : bâtiment F, 2^ème étage, pièce 241
Utilisation : libre-service pour des expériences de routine en journée, et expériences longues la nuit grâce au passeur d'échantillons. (contact : Elsa Caytan)
Historique : aimant et console installés en juillet 2010

RMN Bruker 3OOMHz

Console Avance II
Logiciel d'exploitation : topspin 2.1
Parc de sondes :
- QNP (sonde directe, ¹H, ¹³C, ³¹P, ¹⁹F)
- BBO 5mm (sonde directe large bande)
- BBO 10mm (sonde directe large bande)
- BBI 5mm (sonde inverse large bande avec gradients)
- Sonde triple ¹H, ³¹P et noyaux bas γ
Localisation : bâtiment F,4^ème étage, pièce 442
Utilisation : partagée avec le Laboratoire de Chimie de la Matière Condensée de Paris, et avec le Laboratoire de Chimie des Polymères. (Contact : Geoffrey Gontard)

RMN Bruker 4OOMHz :

Console Avance I
Logiciel d'exploitation : topspin 2.1
Sondes : QNP (sonde directe, ¹H, ¹³C, ³¹P, ¹⁹F + gradients), et SEI (sonde inverse, ¹H, ¹³C + gradients)
Localisation : bâtiment 31, RdC
Utilisation : passeur d'échantillons. (contact : Elsa Caytan)
Historique : console Avance I en 2003, aimant neuf installé en mars 2011

RMN Bruker 250MHz :

Console Avance III nanobay
Logiciel d'exploitation : topspin 2.1
Sonde : SEI (sonde inverse, ¹H, ¹³C + gradients)
Localisation : bâtiment F, 6^ème étage, pièce 656
Utilisation : expériences de routine (contact : Elsa Caytan)
Historique : console installée en mars 2010

Présentation de l'équipe SUPRA

ricci — 2011-01-31T10:18:57Z

L'équipe se consacre à la synthèse et à l'étude d'assemblages multimétalliques fonctionnels avec soit un intérêt biologique, soit des propriétés physiques et chimiques (photo-)activables. Pour cela, nous combinons des complexes de métaux de transition avec des molécules organiques spécifiques.

Cette thématique de recherche est développée selon trois voies complémentaires : i) la réactivité des composés hybrides organiques-inorganiques, ii) la réalisation de complexes photoactifs et iii) l'élaboration par auto-assemblage d'édifices moléculaires fonctionnels. Tous les projets comportent le développement de nouvelles méthodes de synthèse pour produire de manière efficace des composés hybrides. Nos travaux incluent aussi la manipulation des propriétés intrinsèques des molécules par des facteurs extérieurs, par exemple la lumière. Les objectifs sont divers : photocatalyse, effets d'antenne, spintronique moléculaire, reconnaissance moléculaire, marquage et imagerie médicale.

Nous contacter

Pr. Bernold HASENKNOPF

Université Pierre et Marie Curie Paris 6,
4 Place Jussieu, 75252 Paris cedex 5

Bât F 74 4eme ETG case 42
Équipe Chimie Supramoléculaire (SUPRA)

Tel:33(0)1 44 27 32 77
Fax 33(0)1 44 27 38 41

MINI-SYMPOSIUM

ricci — 2010-06-06T22:00:00Z

Lundi 07 juin De 10h à 12h

Carlos Romao (Universidade Nova de Lisboa, Portugal)
Therapy with CO and Metal Carbonyl Drugs
Institut Jacques Monod, (tour 42, rez-de-chaussée)

Michael Sherburn (Australian National University, Canberra Australie)
The Dendralenes : Synthesis, Properties and Applications
Institut Jacques Monod, (tour 42, rez-de-chaussée)