Materiali ibridi auto-organizzati. Joël J.E. Moreau Hétérochimie Moléculaire et Macromoléculaire, UMR CNRS 5076, Ecole Nationale Supérieure de Chimie, 8, rue de l’Ecole Normale, Montpellier (France) Palermo

UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Self-assembly surfactant Condensation Surfactant removal Mesoporous silica UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Templated synthesis of functionalised mesoporous silica surfactant surfactant removal Mesoporous silica with pendant functional groups within the pores UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

TEM image and electron diffraction pattern (inset) of the hybrid mesoporous material with 2D-hexagonal symmetry Templated synthesis of mesoporous bridged silsesquioxanes Inagaki et al JACS, 1999 Inagaki, Stein, Ozin… UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Towards self-assembled hybrid solids Molecular precursor with self-assembly properties UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Self-assembled hybrid solids Is there a possible transcrition of the self-association and self-organisation properties of the organic fragment to the inorganic network? UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Molecular precursors with self-assembly properties Shinkai, Feringa, et al

UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire Chiral molecules with self-assembly properties Chiral organic substruture (R,R) or (S,S) versus racemic mixture Self-assembling by urea groups

UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Solid state NMR of the hybrid silica (acid catalysed hydrolysis in water) 29 Si T2T2 T3T3 13 C UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Helical hybrid silicas: chirality transcription from the precursor molecule to the hybrid solid UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Chirality transcription to form helical hybrid silicas UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Hydrolysis of pure (S,S) enantiomer: (fibrous morphology) width  m and length up to 15  m Hydrolysis of (R,R) (S,S) racemic mixture: (featureless morphology) SEM images of the hybrid silicas (acid catalysed hydrolysis in water) UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Chiral hybrid silica (base catalysed hydrolysis in ethanol/water) UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

T3T3 29 Si 13 C Solid state NMR of the hybrid silica (base catalysed hydrolysis in ethanol/water) UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

SEM images of the hybrid silicas (base catalysed hydrolysis in ethanol/water) Sizes of hollow tubes: Length: up to 15  m External width:  m Size of rectangular channels:  m Thickness of shells:  m UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Longitudinal juxtaposition of fibers (15-25 nm wide) Rough outer surface TEM images of tubular hybrid silicas UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Racemic hybrid silica (base catalysed hydrolysis in ethanol/water) UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Hybrid silica from pure enantiomer R,R or S,S: hollow tubes Hybrid silica from racemic mixture: spheres (0.3-2  m) SEM images of the hybrid silicas (base catalysed hydrolysis in ethanol/water) UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

The reaction was performed in a mixture of ethanol and water (V/V=2/5) 1 – the precursor was first dissolved in ethanol 2 – water was added : white precipitate appeared (microcrystals) 3 – NaOH was added and the mixture was heated at 80°C 4 – the white powder was filtered, washed with water then ethanol 5 – the solid was air-dried at 110 °C Reaction procedure: UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire Mechanism of the formation of the hollow tubular structures

SEM images of micro-crystals formed from R,R-enantiomer Size of the rectangular rods: 2-12 mm long and mm wide Size and shape similarities to the channel of the tubes UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Incipient crystallisation Surface hydrolysis Ethanol formation Solubilisation of the precursor Polycondensation on the outer surface Proposed mechanism for the formation of the tubular structures UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Evidence for the formation of the hollow tubes from TEM studies Dissolution of the precursor After 1 hour reaction: Final material:

Self-assembled molecules combining hydrogen bonding and hydrophobic interactions UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Self-assembled C12 hybrid silica (acid catalysed hydrolysis in water) UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

13 C Solid state NMR of the hybrid silica (acid catalysed hydrolysis in water) T2T2 UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Powder X-ray diffraction of C12 hybrid silica UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

SEM and TEM images of C12 hybrid silica UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

X-ray diffraction of Cn hybrid silicas UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Proposed structure of self assembled C12 hybrid silica UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Polarization dependence of the vibration modes using IRTF-ATR  = 120 cm -1 in the absence of H-bonding C=O = 1618 cm -1  NH = 1583 cm -1  = 35 cm -1 vibration modes : (amide 1, amide 2) Ordered hybrid Amorphous hybrid UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Self-assembled soluble molecules containing aromatic luminescent sustructures UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Organic Gel / Hybrid Gel transcription process UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Birefringent properties of self-assembled organic gel and hybrid gel polarizer ⊜ polarizer ⊕ polarizer ⊗ UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

SEM images of self-assembled organic gel and hybrid gel UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

X-ray diffraction patterns of self-assembled organic gel and hybrid gel UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Blue fluorescence of self-assembled organic gel and hybrid gel Blue fluorescence under UV irradiation at 346 nm UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

New approach for the self-organisation of hybrid materials via the controlled hydrolysis of functional molecules capable of auto-association by H-bond * Chirality transcription from a molecule to the hybrid solid - Right-handed helical fibers from (R,R) enantiomer - Left-handed helical fibers from (S,S) enantiomer * Long range ordered hybrid silica with lamellar morphology. Conclusion * Transcription of the supramolecular organisation in an organogel to a hybrid silica UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

Acknowlegments

Self-Organised Hybrid Silicas with Long Range Ordered Lamellar Structure : Organogel/ Hybrid Gel Transcription Process : Chirality Transcription of Molecular Precursors to Hybrid Silicas: Self-Organised Hybrid Silicas: selected references J.J.E Moreau, L. Vellutini, M. Wong Chi Man and C. Bied J. Am. Chem. Soc , 123, 2001 J.J.E Moreau, B. Pichon, M. Wong Chi Man, C. Bied, J-L Bantignies,P. Dieudonné and J-L Sauvajol, Angew. Chem. Int. Ed , 43, 2004 O. Dautel, J-P. Lère-Porte, J.J.E. Moreau, M. Wong Chi Man Chem. Comm., , 2003 Mechanism of self-structuration: J.J.E Moreau, L. Vellutini, M. Wong Chi Man and C. Bied Chem. Eur. J , 9, 2003 Shaped-Controlled Bridged Silsesquioxanes: J.J.E Moreau, L. Vellutini, M. Wong Chi Man, C. Bied, J-L Bantignies, P. Dieudonné and J-L Sauvajol, J. Am. Chem. Soc., , 123, 2001 UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

The ENSCM at « rue de l’Ecole Normale » A National Graduate School of Chemistry in Montpellier

UV-Visible absorption and emission spectra of molecular precursor and hybrid gel UMR CNRS 5076: Hétérochimie Moléculaire et Macromoléculaire

OR OH HO RO HO OR OH HO RO HO OR OH HO RO HO Si(OR) 3 (HO) 2 ROSi SiOR(OH) 2 HO(RO) 2 Si Si(OR ) 2 OH (HO) 2 ROSi (OR) 3 S i S i S i S i O H O O O O RO OR (OR) 2 S i S i O S i (RO) 2 S i O (OR) 2 HO OH Mechanism of the formation of the hollow tubular structures