Supramolecular Chemistry and Nanomaterials

6 EC

Semester 1, period 1

5254SUCN6Y

Owner Master Chemistry (joint degree)
Coordinator dr. R.M. Williams
Part of Master Chemistry (joint degree), track Molecular Sciences,
Links Visible Learning Trajectories

Course manual 2024/2025

Course content

Supramolecular chemistry
The course lays down the basic principles of supramolecular chemistry: molecular self-assembly by using non-covalent interactions, such as hydrogen-bonding, hydrophobic forces, metal coordination and π-π interactions. Molecular self-organization, pre-organization, templating and self-organized growth are exemplified. Host-guest complexes that are made up of two or more parts and are held together through non-covalent interactions, which can reversibly bind and dissociate are also studied. A special topic in supramolecular chemistry is formed by mechanically interlocked molecular structures, such as rotaxanes and catenanes that are bound as a result of their topology. Supramolecular catalysis forms an important aspect of the course. Thermodynamic aspects as well as the importance of the molecular environment in supramolecular chemistry are discussed as well as the synthesis and characterization of artificial supramolecular assemblies.

Nanomaterials.
The concepts in supramolecular chemistry for synthesis of supramolecular constructs are prevalent in nanotechnology and nano-science. Self-assembly is one of the options to make nano-structures. Quantum dots, nanoparticles and various applications of nanomaterials including medicine, catalysis and (organic) photovoltaïcs are discussed. Photo-active  molecular motors are examplified with the work of Feringa and Stoddart. One focus is on fast spectroscopy in supramolecular chemistry and photo-active nanomaterials. Various time-resolved techniques are exemplified in order to understand more about photoinduced processes, excited states in supramolecular systems, rates and mechanisms of different photochemical processes. This part ends with an introduction to nanotechnology. Nanomaterials are composed of (molecular) units and have features on the 1-100 nm scale that determine their function, and behave different from the bulk. Examples of functional photo-active nanomaterials are discussed.

Study materials

Literature

  • Jonathan W. Steed, Jerry L. Atwood, 'Supramolecular Chemistry', 2nd Edition; ISBN: 978-1-118-68150-3 Chapters 1, 2, 6, 9, 10, 11, 12, 15. The first four are introductory, the last four are the specialized topics. http://onlinelibrary.wiley.com/book/10.1002/9780470740880 (e-book available within UvA or VU domain.)
  • C.A. Hunter, 'Quantifying molecular interactions: Guidelines for the molecular recognition toolbox', Angewandte Chemie, 43 5310-5324, 2004. http://dx.doi.org/10.1002/anie.200301739 (available within UvA or VU domain.)

Objectives

  • Use molecular building blocks to design functional (photo-active) supramolecular constructs and nano-structured materials by using the principles of Supramolecular Chemistry.
  • Describe the molecular basis of the formation and (photo)-functioning of supramolecular assemblies and nanomaterials.
  • Quantify molecular interactions by using the molecular recognition toolbox developed by Hunter (functional group interactions diagrams) with respect to Gibbs free energy change and complex formation constants.
  • Select a specific type of (time-resolved) spectroscopy to study interactions between different groups in supramolecular assemblies and photo-active nanomaterials and design experiments to quantify these (photoinduced) interactions.
  • Present clearly and concisely a (recent) scientific paper on supramolecular chemisty or on nanomaterials/nanoscience (to the fellow-students).
  • Use creativity with respect to developing new scientific concepts and scientific research topics.
  • Write an original research proposal describing new ideas and concepts that in principle could be the basis of a PhD research in the area of supramolecular chemistry Or in the area of nanomaterials (you can start working on it now!!). Making this assignment is mandatory!
  • Apply the outcome of time-resolved spectroscopic studies to understand and analyze the functioning of photo-active supramolecular assemblies and photo-active nanomaterials.
  • Get insight into the factors playing a role in the formation of the kinetic reaction product vs the thermodynamic reaction product and be able to discriminate between them.
  • Envisage emergent properties upon combination of different supramolecular components.
  • Apply analytical tools to understand Supramolecular systems.
  • Understand the thermodynamic concepts behind dynamic covalent systems.
  • Learn How to apply H-bond motifs to create functional materials.
  • Develop understanding of the relation between nanostructure in organic photovoltaic materials and the efficiency of the related solar cell devices, and knowledge on how to influence these nano-structures.
  • Describe and use the photo-physical basis of the formation charge separated states in supramolecular assemblies and nanomaterials by applying the Marcus Theory of Electron Transfer.
  • Design experiments to quantify photoinduced interactions in supramolecular assemblies and nanomaterials.

Teaching methods

  • Lecture
  • Seminar
  • Presentation/symposium

Lectures and tutorials.

Assignments that have to be uploaded via Canvas.

Presentations by the students.

Suggestions will be given but you can choose a scientific paper yourself to present during the course (we have to approve your choice at the beginning of/during the course). It should be about 'Supramolecular Chemistry' or about 'Nanomaterials'. We recommend 'Science' or 'Nature' papers. But, other journal are also possible.

Learning activities

Activity

Number of hours

Hoorcollege

26

Tentamen

3

Zelfstudie

139

Attendance

This programme does not have requirements concerning attendance (TER part B).

Assessment

Item and weight Details

Final grade

1 (100%)

Tentamen

The exam makes up 65% of the final grade, and contains 4 questions.

The assignment of the research proposal that has to be uploaded makes up 20%.

The presentation at the symposium makes up 10%.

The assignments that have to be uploaded make up 5%.

Fraud and plagiarism

The 'Regulations governing fraud and plagiarism for UvA students' applies to this course. This will be monitored carefully. Upon suspicion of fraud or plagiarism the Examinations Board of the programme will be informed. For the 'Regulations governing fraud and plagiarism for UvA students' see: www.student.uva.nl

Course structure

 

Basics and Introduction

Introduction to the course structure

Introduction to Supra and Nano

Molecular Motors

Complexation

Applications in solution

Fast spectroscopy

Metal organic cages

Supramolecular catalysis

hydrogen bonding

Applications in solids

Dye sensitized solar cells

Bioinspired Self-assembly for Functional Materials

Organic Solar Cells

Functional Nanotechnology

 

 

 

 

General introduction to supramolecular chemistry, bonding/interactions in supramolecular chemistry, thermodynamics of supramolecular assemblies, analytical methods

Literature: Chapter 1 and 2, 10.4, 10.7

 

Connecting nanotechnology to Supramolecular chemistry

Chapter 1, (page 1-45);

Chapter 10 (page 591-697);

Chapter 13, page 837-839

Chapter 6, page 320-321

 

Molecular Motors

Chapter 10, page 653-677, 691-697

Chapter 11, page 752-765

 

Complexation, equilibrium and basic thermodynamics;

A simple model to estimate binding strength (Hunter);

Experimental characterization of binding.

Literature references in slides and Chapter 3, Chapter 4, 10.4,

C. A. Hunter, Quantifying Intermolecular Interactions: Guidelines for the Molecular Recognition Toolbox, Angew. Chem. Int. Ed. 2004, 43, 5310-5324.

 

Fast spectroscopy in Supramolecular Chemistry and Nanomaterials

Introduction to Photo-active Nanomaterials: The Nature of excited states

Chapter 11. page 707-771

and

https://www.researchgate.net/publication/225188430_Introduction_to_Electron_Transfer

or (same document from different source)

http://www.uva.nl/binaries/content/documents/personalpages/w/i/r.m.williams/en/tab-one/tab-one/cpitem%5B22%5D/asset?1355372849366

 

 

Model validation;

Host-guest systems for ionic and neutral species;

Hydrogen-bond based assemblies & cooperativity

Literature references in slides and Chapter 6

A. Mulder, J. Huskens, D. N. Reinhoudt, Multivalency in supramolecular chemistry and nanofabrication, Org. Biomol. Chem., 2004, 2, 3409-3424.

 

 

Larger self-assemblies based on hydrogen bonding

Hydrogen bonded capsules

Supramolecular polymers

Chapter 10.6, lecture slides and papers provided on canvas

 

 

Coordination chemistry and organometallic chemistry as tool in supramolecular chemistry.

Metal organic cages (MOC

Metal based nanaospheres.

Chapter 9.5, lecture slides and papers provided on canvas

  

 

Supramolecular catalysis

Chapter 6, lecture slides and papers provided on canvas

 

Organic Solar Cells: photo-generation of free charges, molecular organization and fast spectroscopy

http://onlinelibrary.wiley.com/doi/10.1002/anie.200702506/abstract

and

http://pubs.rsc.org/is/content/articlehtml/2009/ee/b812502n

 

 

Dye sensitized solar cells

https://doi.org/10.1039/C8TC03542C

 

Bioinspired Self-assembly for Functional Materials

https://doi.org/10.1126/science.aah6350

 

 

Functional nanotechnology.

chapter 15 (page 900-937).

 

 

 

 

Contact information

Coordinator

  • dr. R.M. Williams

Staff

  • prof. dr. Joost Reek