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3 Mesochemistry Lecture 1
3 Mesochemistry Lecture 1
INORGANIC CHEMISTRY
MESOCHEMISTRY
SYNTHESIS IN “INTERMEDIATE” DIMENSIONS
Geoffrey A. Ozin
Materials Chemistry Research Group
University of Toronto
ISI Citations
6386
(scopus2019:14230)
ESCAPE FROM 10 Å PRISON
• Discovery by Mobil
researchers that an assembly
of surfactant molecules could
function as a supramolecular
template for organizing and
polymerizing silicates
• Produced the first fully
characterized examples of
periodic hexagonal and cubic
forms of mesoporous silica
with pore diameters 2-10 nm
• Integration of surfactant and
sol-gel chemistry
Air drying
SOL-GEL CHEMISTRY
SC CO2 drying
SOL-GEL CHEMISTRY
Air drying
SOL-GEL CHEMISTRY
Base catalyzed hydrolytic poly-condensation of silicon alkoxides to silica
SOL-GEL CHEMISTRY
Acid catalyzed hydrolytic poly-condensation of silicon alkoxides to silica
• HYDROLYSIS
• CONDENSATION
EFFECT ON SELF-
ASSEMBLY MECHANISM
Surfactant
Catalyst Temperature
Concentration
pH
Precursor Template removal
Ageing conditions
HYDROLYSIS, CONDENSATION, SELF-ASSEMBLY
ESCAPE FROM 10 Å PRISON
100
110
200
210
Macroporous > 50 nm
cubic
Microporous < 2 nm
Mesocrystalline glass –
crystalline mesoporosity
- periodic arrangement
of mesopores – glassy
walls - long range order
Cubooctahedral morphology at mesoscale – short
range order at
microscale
WHAT CAN WE DO WITH PMS MATERIALS?
HOST-GUEST INCLUSION WITH LARGE GUESTS !!!
ORGANICALLY FUNCTIONALIZED
PMS - GRAFTING
CLEVER USE OF GRAFTING CONTROLLED
RELEASE OF ACTIVE COMPOUNDS
NANO-PMS
SMART DRUG
DELIVERY
AFM 2007
ORGANICALLY FUNCTIONALIZED
PMS - COCONDENSATION
PHOTOCHEMICAL SWITCH
PORE SIZE CONTROL
Periodic mesoporous silica with channel walls functionalized with terminally bound
alkanethiol groups that chelate and sequester toxic heavy metals.
PERIODIC MESOPOROUSN
ORGANOSILICAS PMOs
ZOO OF PMO PRECURSORS
Acc. Chem. Res. 2005, 38, 305-312.
https://www.nature.com/articles/am201413
MATERIALS CHEMISTRY SOLUTION
TO THE LOW k CHALLENGE
Periodic mesoporous
organosilicates PMOs with
organic cross-links!!!
Hatton, B.D., Landskron, K., Hunks, W.J., Bennett, M.R., Shukaris, D., Perovic, D.D., Ozin, G.A., New Materials Chemistry
Approaches for Low Dielectric Constant Materials as Interlayer Dielectrics, Materials Today 2006, 9, 22.
METAMORPHIC CHANNEL WALLS – PMO BRIDGE
TERMINAL EXCHANGE
PMO WITH ORDERED BRIDGING AROMATIC
GROUPS IN THE CHANNEL WALLS
MOLECULAR MODEL OF THE ORDERING OF BRIDGING BENZENE
GROUPS IN THE CHANNEL WALL OF BENZENE PMO
MOLECULAR MODEL OF THE ORDERING OF BRIDGING THIOPHENE
GROUPS IN THE CHANNEL WALL OF THIOPHENE PMO
BIFUNCTIONAL PMOs
The Idea – PMO to MIPMO
IMPRINT IMPRINT
IMPRINT
the idea
imprint
molecule
imprint
removal
collaboration
Jean-Christophe Leroux (CRC in Drug Delivery)
Diltiazem Verapamil
Drug Silsesquioxanes
MESOPOROUS MATERIALS
GRAND CHALLENGES – UTILITY