Instructor: Dr. Marinella Sandros

1. Nanochemistry NAN 601 • Instructor: • Dr. MarinellaSandros Lecture 8: Supramolecular Chemistry

2. What is Supramolecular Chemistry ? “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” J.-M- Lehn "Supramolecular chemistry is defined as chemistry ‘beyond the Molecule’, as chemistry of tailor shaped inter-molecular interaction.” F. Vögtle http://www.waltry.f2s.com/lectures/supra-lec1.pdf

3. What is Supramolecular Chemistry? • “Chemistry beyond the molecule” • “Chemistry of molecular assemblies and of the intermolecular bond.” • “The Chemistry of non-covalent bond.”

4. Supramolecular chemistry involves investigating molecular systems in which the most important feature is that components are held together by intermolecular forces, not by covalent bonds. Atoms Molecules Molecules Supermolecules Covalent Interactions Non-Covalent Interactions

5. Supramolecular Chemistry http://www.tfp.uni-karlsruhe.de/Summerschool/Lectures/voegtle1.pdf

6. Supramolecular Chemistry • Where did it come from? Inspired from biology and built on the shoulders of traditional synthetic organic chemistry. • Why does it deserve to be a field of study all its own? The next logical step in synthetic chemistry; understanding and interface with the biological world; nanotechnology http://www.waltry.f2s.com/lectures/supra-lec1.pdf

7. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

8. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

9. Lock and Key Principle http://www.waltry.f2s.com/lectures/supra-lec2.pdf

11. Beyond Host/Guest Chemistry • Molecular Self-Assembly: Process by which 2 or more molecules interact from a larger structure or organization. • Super-Molecule: A complex formed by molecular self-assembly which contains a discrete number of subunits. http://www.waltry.f2s.com/lectures/supra-lec2.pdf

12. Covalent Bond Energies http://www.waltry.f2s.com/lectures/supra-lec2.pdf

13. Non-Covalent Interactions: Electrostatic

14. Hydrogen-Bonded Interactions

15. Hydrogen Bond http://www.waltry.f2s.com/lectures/supra-lec2.pdf

16. -  Interactions http://www.waltry.f2s.com/lectures/supra-lec2.pdf

17. Dispersion Forces http://www.waltry.f2s.com/lectures/supra-lec2.pdf

18. Hydrophobic Effect http://www.waltry.f2s.com/lectures/supra-lec2.pdf

19. Coordination Bonds http://www.waltry.f2s.com/lectures/supra-lec2.pdf

20. Supramolecular: Biology • The study of non-covalent interactions is crucial to understanding many biological processes from cell structure to vision that rely on these forces for structure and function. Biological systems are often the inspiration for supramolecular research. http://en.wikipedia.org/wiki/Supramolecular_chemistry

21. Example :DNA

22. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

23. How to make a receptor ? people.bio.aau.dk/.../PowerPoint/Supramolecular%20chemistry.ppt

24. Biotin-Streptavidin malina.ichf.edu.pl/educ/.../WYKLAD_SUPRA_NANO1_2005.ppt

25. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

26. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

27. Answer??? http://www.waltry.f2s.com/lectures/supra-lec1.pdf

28. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

29. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

30. Forces Involved in Self-Assembly: http://www.waltry.f2s.com/lectures/supra-lec1.pdf

31. Interaction Energies http://www.waltry.f2s.com/lectures/supra-lec1.pdf

32. Chelate Effect • Two donor atoms linked together = a chelate (claw) • Chelate ligands form much more stable metal complexes than monodentate related ligands (up to 105 times as stable) • Ni2+ + L Formation Constants: • L = NH3 en trien 2,3,2 • 8.12 13.54 13.8 16.4 better complementarity faculty.swosu.edu/tim.hubin/InorganicLects/InorgCh12.2.ppt

33. Chelate Effect Why is favorable?? Thermodynamic Reasons for the Chelate Effect = Entropy

34. Macrocylic Effect Macrocyclicchelate complexes are up 107 times more stable than non-cyclic chelates with the same number of donors • Ni(trien)2+ + H+ Ni2+ + H4trien4+ t½ = 2 seconds • Ni(cyclam)2+ + H+ Ni2+ + H4cyclam4+ t½ = 2 years • Connecting all of the donors (having no end group) makes k-2 important • Breaking the first M—L bond requires major ligand deformation • The increase in Ea required greatly slows down k-2 faculty.swosu.edu/tim.hubin/InorganicLects/InorgCh12.2.ppt

35. Macrocylic Effect • The result is a very stable complex as kd becomes miniscule

36. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

37. Valinomycin http://www.waltry.f2s.com/lectures/supra-lec1.pdf

38. Self-Assembly http://www.ciam.unibo.it/photochem/Ri.mo_03.pdf

39. Supramolecular Assembly • They allow access to nanoscale objects using a bottom-up approach in far fewer steps than a single molecule of similar dimensions. • The process by which a supramolecular assembly forms is called molecular self-assembly. Some try to distinguish self-assembly as the process by which individual molecules form the defined aggregate. Self-organization, then, is the process by which those aggregates create higher-order structures. http://en.wikipedia.org/wiki/Supramolecular_assembly

40. http://www.ciam.unibo.it/photochem/Ri.mo_03.pdf

41. Self-Organization and Self-Assembly http://www.ciam.unibo.it/photochem/Ri.mo_03.pdf

42. Important Features http://www.ciam.unibo.it/photochem/Ri.mo_03.pdf

43. Molecular Imprinting http://www.esonn.fr/0oldweb/ESONN04/Lectures/esonn_2004_Mascini3.pdf

44. Imprinted Polymer-coated QCM Sensors

45. Molecular Imprinted Polymers http://www.google.com/search?client=safari&rls=en&q=molecular+imprinting+ppt&ie=UTF-8&oe=UTF-8