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Supramolecular Chemistry
http://homepage.univie.ac.at/jeanluc.mieusset/teaching.html
Supramolecular Chemistry 1 - Concepts.pdf
Supramolecular Chemistry 2 - Cation binding.pdf
Supramolecular Chemistry 3 - Binding of anions.pdf
Supramolecular Chemistry 4 - Neutral molecules.pdf
Supramolecular Chemistry 5 - Methods.pdf
Supramolecular Chemistry 6 - Self-Assembly.pdf
Supramolecular Chemistry 7 - Artificial enzyms.pdf
Supramolecular Chemistry 8 - Molecular Devices.pdf
Supramolecular Chemistry 9 - Molecular Machines.pdf
Supramolecular Chemistry 10 - New.pdf
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Supramolecular Chemistry
Steed, J. W.; Atwood, J. L.Supramolecular Chemistry,
Wiley 2000 $ 40,- Balzani, V.; Venturi, M.; Credi, A.
Molecular Devices and MachinesWiley VCH 2003
Schneider, H.-J.; Yatsimirski, A.Principles and Methods in Supramolecular ChemistryWiley 2000 39,95
Comprehensive Supramolecular Chemistry, Vol. 1-10;Lehn, J.-M., Series editor,
Pergamon/Elsevier Oxford etc, 1996 $ 425 per volume Encyclopedia of Supramolecular Chemistry
edited by Jerry L. Atwood and Jonathan W. SteedDekker, 2004 1,500 pages $489.00
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What is Supramolecular Chemistry?
MULTIDISCIPLINARY FIELD
NATURE (biological systems) - inspiration
ORGANIC and INORGANIC CHEMISTRY building blocks(supramolecular synthons)
PHYSICAL CHEMISTRY methods to study and understand theirproperties
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What is Supramolecular Chemistry?
The ultimate supramolecular material?
Held together by many specifichydrogen bonds, - stacking, etc.
Encodes gigabytes of data Can Self-Replicate
Built-in Error Correction Information Storage Is the basis of life
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What is Supramolecular Chemistry?
Tobacco Mosaic Virus (TMV)
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What is Supramolecular Chemistry?
Actin-Myosin Complex
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What is Supramolecular Chemistry?
Kinesin Crawling Along a Microtubule
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What is Supramolecular Chemistry?
MOLECULAR CHEMISTRY covalent bonds formation
SUPRAMOLECULAR CHEMISTRY non-covalent bond formation
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What is Supramolecular Chemistry?
J. M. Lehn:
Supramolecular chemistry is the chemistry of the intermolecular
bond, covering the structures and functions of the entities formed bythe association of two or more chemical species
F. Vgtle:In contrast to molecular chemistry, which is predominantly basedupon the covalent bonding of atoms, supramolecular chemistry is
based upon intermolecular interactions, i.e. on the association of twoor more building blocks, which are held together by intermolecularbond
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What is Supramolecular Chemistry?
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What is Supramolecular Chemistry?
But also:
Molecular Devices
Supramolecular Photochemistry
Electronic Switches
Dendrimers
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What is Supramolecular Chemistry?
Top-Down (current technology).
Continued reduction in size of bulk semiconductor devices
optical, ultra-violet, ion-beam, electron-beam lithography
Bottom-Up (molecular scale electronics).
Design of molecules with specific electronic function
Design of molecules for self-assembly into supramolecular structures
Connecting molecules to the macroscopic world
Man-made synthesis (e.g. carbon nanotubes)
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What is Supramolecular Chemistry?
1-50 nm 1-500 nm
Supramolecular
Aggregates
Nanoelectronics
nanobiology
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Development - History
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Development - History
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Classification of Host-Guest Compounds
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Classification of Host-Guest Compounds
Spherand
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Classification of Host-Guest Compounds
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Corpora non agunt nisi fixata
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Receptors and the Lock and Key Analogy
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The Chelate and Macrocyclic Effects
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The Chelate and Macrocyclic Effects
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The Chelate and Macrocyclic Effects
Less entropically favorable
Stabilization offered by the chelate effect
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Preorganization and Complementarity
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Preorganization and Complementarity
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Nature of Supramolecular Interactions
Covalent bond energies:
C-O bond 340kJ / mol 1.43C-C bond 360kJ / mol 1.53C-H bond 430kJ / mol 1.11C=C bond 600kJ / mol 1.33
C=O bond 690kJ / mol 1.21
Compared to most non-covalent interactions these are:
Very high energies Very short distances Highly dependant on orientation
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Nature of Supramolecular Interactions
Driving Forces for the Formation of Supramolecular Structures
hydrophobic interaction
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Nature of Supramolecular Interactions
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Nature of Supramolecular Interactions
Ion - Ion Interactions
Can be a very strong bond - even stronger then covalent bonds in somecases.
Can be an attractive or a repulsive force.
Non-directional force
Long range (1/r)
Highly dependant on the dielectric constant of the medium
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Nature of Supramolecular Interactions
IonIonIonIonInteractionsInteractions
Energy = (k * z1 * z2 * e2) / ( r12)
k = 1 / 4o= Coulomb constant = 9*109Nm2/C2
e = elementary charge = 1.6*10-19C
= dielectric constant
r12 = meters between the objects
The energy of an ion-ion interaction only falls of at a rateproportional to 1 / r. Therefore these are very long range
forces.
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Nature of Supramolecular Interactions
IonIonIonIonInteractionsInteractions
1 nm in water?
1 nm in Chloroform?
Energy = (k * z1 * z2 * e2) / ( r12)
= 9*109 * 1 * -1 * (1.6*10-19)2/ 78.5 * 1 * 10-9
= -2.3 * 10 -28/ 0.8 * 10 -7
= -29.4 * 10-22 J= -1.77 kJ / mole (-0.42 kcal / mole)
= 9*109 * 1 * -1 * (1.6*10-19)2/ 4.8 * 1 * 10-9
= -2.3 * 10 -28/ 4.8 * 10-9
= -4.79 * 10-20 J= -28.8 kJ / mole (-6.89 kcal / mole) -> 8% of a C-C bond
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Nature of Supramolecular Interactions
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Nature of Supramolecular Interactions
Energy = -(k * Q * u * cos/ e * r2)If = zero= -k * Q * u / e * r2
= -9*109 * 1.6*10-19 * 2.9 * 3.336 *10-30/ e * r2= -1.39 * 10-38 / 4.8 * (10-9)2
= -2.9 * 10-21 J= -1.75kJ / mole
Example: Acetone pointing directly at Na ion ( = zero) ata distance of 1nm (in chloroform)
IonIon--Dipole InteractionDipole Interaction
u = q * l (dipole moment)l = length of the dipoleq = partial charge on dipoler = distance from charge tocenter of dipoleQ = charge on ion
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Nature of Supramolecular Interactions
IonIon--Dipole InteractionDipole Interaction
Directional forces
Can be attractive or repulsive
Medium range (1/r2)
Significantly weaker then ion-ioninteractions
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Nature of Supramolecular Interactions
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Nature of Supramolecular Interactions :
Hydrogen Bonding
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Nature of Supramolecular Interactions :
Hydrogen Bonding
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Nature of Supramolecular Interactions :
Hydrogen Bonding
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Nature of Supramolecular Interactions :
Hydrogen Bonding
Van der Waals radius of H: 1.1, O1.5. Therefore closest approachshould be 2.6.
Actual separation is about 1 less!Distance of 1.76.
Intermediate between vdw distance andtypical O-H covalent bond of 0.96.
O H O
R
RH
O
H O R
RH
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Nature of Supramolecular Interactions :
Hydrogen Bonding
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Nature of Supramolecular Interactions :
Hydrogen Bonding
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Nature of Supramolecular Interactions :
Hydrogen Bonding
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Nature of Supramolecular Interactions :
Halogen Bonding
Halogen atoms iodine, bromine, chlorine and even fluorine can
function as Lewis acids and engage in electron donor-acceptor
interactions with atoms with lone pairs such as nitrogen, oxygen,phosphorus and sulfur.
BIX-
Halogen bonding may involve dihalogenes X2 and X-Y as well as
organic halides
The strength of the donor-acceptor interaction depends on thepolarizability of the halogen atom, decreases in the order:
I > Br > Cl (> F)
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Nature of Supramolecular Interactions :
Halogen Bonding
DMSO to haloarene halogen bondinggeometry:
head on to C-X, ~ 158(13)(Cl),162(12)(Br), and ~165(8)(I);
side on to S=O,
: 125-135.
Increase of polarity of the both C-Xand S=O bond increases the strengthof interaction:
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Nature of Supramolecular Interactions :
The Cation Interaction
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Nature of Supramolecular Interactions :
Stacking
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Nature of Supramolecular Interactions :
Stacking
N f S l l I i
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Nature of Supramolecular Interactions :
Stacking
N t f S l l I t ti
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Nature of Supramolecular Interactions :
Interactions
Chem. Rev. 2000,100, 4145-4185.
N t f S l l I t ti
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Nature of Supramolecular Interactions :
Charge-Transfer Complex
Nature of Supramolecular Interactions :
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Nature of Supramolecular Interactions :
Van der Waals Forces
Strength of interaction is essentially a function of the surface area ofcontact. The larger the surface area the stronger the interaction will be.
Regardless of other interactions found within a complex there will almost
always be a contribution from vdw.
This is what drives molecules to eliminate spaces or vacuums and makes itdifficult to engineer porous or hollow structures and gives rise to the phrase
Nature abhors a vacuum.
Nature of Supramolecular Interactions :
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Nature of Supramolecular Interactions :
Van der Waals Forces
Nature of Supramolecular Interactions :
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Nature of Supramolecular Interactions :
CLOSE PACKING IN THE SOLID STATE
Conformers allowing maximum intermolecular
interactions, even very weak (which do not play a rolein solution)
Empty space: crystal pores and channels -> inclusioncrystals
TETRIS analogy
Nature of Supramolecular Interactions :
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Nature of Supramolecular Interactions :
Hydrophobic Effects
Nature of Supramolecular Interactions :
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Nature of Supramolecular Interactions :
Hydrophobic Effects
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