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

Supramolecular Chemistry
Steed, J. W.; Atwood, J. L. Supramolecular Chemistry, Wiley 2000 $ 40,Balzani, V.; Venturi, M.; Credi, A. Molecular Devices and Machines Wiley VCH 2003 Schneider, H.-J.; Yatsimirski, A. Principles and Methods in Supramolecular Chemistry Wiley 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. Steed Dekker, 2004 1,500 pages $489.00

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 their properties

What is Supramolecular Chemistry?

The ultimate supramolecular material? Held together by many specific hydrogen bonds, - stacking, etc. Encodes gigabytes of data Can Self-Replicate Built-in Error Correction Information Storage Is the basis of life

What is Supramolecular Chemistry?

Tobacco Mosaic Virus (TMV)

What is Supramolecular Chemistry?

Actin-Myosin Complex

What is Supramolecular Chemistry?

Kinesin Crawling Along a Microtubule

What is Supramolecular Chemistry?

MOLECULAR CHEMISTRY covalent bonds formation SUPRAMOLECULAR CHEMISTRY non-covalent bond formation

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 by the association of two or more chemical species F. Vgtle: In contrast to molecular chemistry, which is predominantly based upon the covalent bonding of atoms, supramolecular chemistry is based upon intermolecular interactions, i.e. on the association of two or more building blocks, which are held together by intermolecular bond

What is Supramolecular Chemistry?

What is Supramolecular Chemistry?

But also: Molecular Devices Supramolecular Photochemistry Electronic Switches Dendrimers

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)

What is Supramolecular Chemistry?

Supramolecular Aggregates 1-50 nm 1-500 nm Nanoelectronics nanobiology

Development - History

Development - History

Classification of Host-Guest Compounds

Classification of Host-Guest Compounds

Spherand

Classification of Host-Guest Compounds

Corpora non agunt nisi fixata

Receptors and the Lock and Key Analogy

The Chelate and Macrocyclic Effects

The Chelate and Macrocyclic Effects

The Chelate and Macrocyclic Effects

Less entropically favorable

Stabilization offered by the chelate effect

Preorganization and Complementarity

Preorganization and Complementarity

Nature of Supramolecular Interactions

Covalent bond energies: C-O bond C-C bond C-H bond C=C bond C=O bond 340kJ / mol 360kJ / mol 430kJ / mol 600kJ / mol 690kJ / mol 1.43 1.53 1.11 1.33 1.21

Compared to most non-covalent interactions these are: Very high energies Very short distances Highly dependant on orientation

Nature of Supramolecular Interactions

Driving Forces for the Formation of Supramolecular Structures hydrophobic interaction electrostatic interaction hydrogen bond interaction van der Waals interaction cation interaction stacking <40 kJ/mol ~20 kJ/mol 12-30 kJ/mol 0.4-4 kJ/mol 5-80 kJ/mol 0-50 kJ/mol

The total inter-molecular force acting between two molecules is the sum of all the forces they exert on each other.

Nature of Supramolecular Interactions

Nature of Supramolecular Interactions

Ion - Ion Interactions Can be a very strong bond - even stronger then covalent bonds in some cases. Can be an attractive or a repulsive force. Non-directional force Long range (1/r) Highly dependant on the dielectric constant of the medium

Nature of Supramolecular Interactions

IonIon Interactions

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 rate proportional to 1 / r. Therefore these are very long range forces.

Nature of Supramolecular Interactions

IonIon Interactions 1 nm in water? 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) 1 nm in Chloroform? = 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

Nature of Supramolecular Interactions

Nature of Supramolecular Interactions

Ion-Dipole Interaction

Example: Acetone pointing directly at Na ion ( = zero) at a distance of 1nm (in chloroform)

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

u = q * l (dipole moment) l = length of the dipole q = partial charge on dipole r = distance from charge to center of dipole Q = charge on ion

Nature of Supramolecular Interactions

Ion-Dipole Interaction

Directional forces Can be attractive or repulsive Medium range (1/r2) Significantly weaker then ion-ion interactions

Nature of Supramolecular Interactions

Nature of Supramolecular Interactions : Hydrogen Bonding

Nature of Supramolecular Interactions : Hydrogen Bonding

Nature of Supramolecular Interactions : Hydrogen Bonding

Nature of Supramolecular Interactions : Hydrogen Bonding

R O H

H O R

Van der Waals radius of H: 1.1, O 1.5. Therefore closest approach should be 2.6.

R O H

H O R

Actual separation is about 1 less! Distance of 1.76. Intermediate between vdw distance and typical O-H covalent bond of 0.96.

Nature of Supramolecular Interactions : Hydrogen Bonding

Nature of Supramolecular Interactions : Hydrogen Bonding

Nature of Supramolecular Interactions : Hydrogen Bonding

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. BIXHalogen bonding may involve dihalogenes X2 and X-Y as well as organic halides The strength of the donor-acceptor interaction depends on the polarizability of the halogen atom, decreases in the order: I > Br > Cl (> F)

Nature of Supramolecular Interactions : Halogen Bonding

DMSO to haloarene halogen bonding geometry: 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-X and S=O bond increases the strength of interaction:

Nature of Supramolecular Interactions : The Cation Interaction

Nature of Supramolecular Interactions : Stacking

Nature of Supramolecular Interactions : Stacking

Nature of Supramolecular Interactions : Stacking

Nature of Supramolecular Interactions : Interactions

Chem. Rev. 2000,100, 4145-4185.

Nature of Supramolecular Interactions : Charge-Transfer Complex

Nature of Supramolecular Interactions : Van der Waals Forces

Strength of interaction is essentially a function of the surface area of contact. 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 it difficult to engineer porous or hollow structures and gives rise to the phrase Nature abhors a vacuum.

Nature of Supramolecular Interactions : Van der Waals Forces

Nature of Supramolecular Interactions :

CLOSE PACKING IN THE SOLID STATE

Conformers allowing maximum intermolecular interactions, even very weak (which do not play a role in solution) Empty space: crystal pores and channels -> inclusion crystals TETRIS analogy

Nature of Supramolecular Interactions : Hydrophobic Effects

Nature of Supramolecular Interactions : Hydrophobic Effects