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, year 1

Course manual 2017/2018

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.
This part begins 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 nanomaterials are discussed. 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 especially (organic) photovoltaics are discussed. The final part of the course concentrates on fast spectroscopy in supramolecular chemistry and (photovoltaic)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. Limitations of photovoltaics are also 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

After following this course, the student is able to:

  • use molecular building blocks to design functional supramolecular constructs and nano-structured materials by using the principles of Supramolecular Chemistry.
  • describe the molecular (and photo-physical) basis of the formation and functioning of (photoactive) 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 and quantify interactions between different groups in supramolecular assemblies and nanomaterials and design experiments to determine 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 (this is in fact exam question 1; you can start working on it now!!). Answering this first exam question is mandatory!

Teaching methods

  • Lecture
  • Seminar
  • Presentation/symposium

Lectures and tutorials. Presentations by the students.

Suggestions will be given but you can choose a scienctific 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

The programme does not have requirements concerning attendance (OER-B).

Assessment

Item and weight Details

Final grade

0.9 (90%)

Tentamen

0.1 (10%)

Presentatie

Deze verdeling gaat in voor de 2018-2019 editie van dit vak!

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

Lectures Reek/Mooijbroek: Supramolecular Chemistry

Lecture 1

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

Literature: Chapter 1 and 2

 

Lecture 2

Host-guest chemistry (Cation and anion binding), Cooperativity, Allosteric effects, Multivalency Hydrogen-bond based assemblies

Literature: Chapter 3, Chapter 4

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

 

Lecture 3

Recognition of organic molecules, Hunter model for quantification of molecular interactions, Measuring of binding constants

Literature: Chapter 6

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

 

Lecture 4

Book chapters: 9.5, 10.5

Review papers from Stang and fujita?? specify

 

Lecture 5

Supramolecular polymers, Molecular capsules, DCC

Chapter 14

Hof, S. L. Craig, C. Nuckolls, J. Rebek, Molecular Encapsulation, Angew. Chem. Int. Ed. 2002, 41, 1488-1508.

M. Conn, J. Rebek, Self-Assembling Capsules, Chem. Rev. 1997, 97, 1647-1668.

J. Rowan, S. J. Cantrill, G. R. L. Cousins, J. K. M. Sanders, J. F. Stoddart, Dynamic Covalent Chemistry, Angew. Chem. Int. Ed. 2002, 41, 898-952.

T. Corbett, J. Leclaire, L. Vial, K. R. West, J.-L. Wietor, J. K. M. Sanders, S. Otto, Dynamic Combinatorial Chemistry, Chem. Rev. 2006, 106, 3652-3711

 

Lecture 6

  • Meeuwissen and J.N.H Reek*, “New directions in supramolecular catalysis,” Nature Chemistry, 2010, 2, 615
  • Dydio, J.N.H. Reek*, “Supramolecular control of selectivity in transition-metal catalysis through substrate preorganization” Chem. Sci, 2014, 5, 2135.
  • H.A.M., Leenders, R. Gramage-Doria, B. de Bruin, J.N.H. Reek*, “Transition metal catalysis in confined spaces” Chem. Soc. Rev, 2015, 44, 433 - 448

 Book Chap 12 p 778-792 p813-825

 

Lectures Williams: Nanomaterials

Lecture 1

Introduction to nanotechnology.

chapter 15 (page 900-937).

 

Lecture 2

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

 

 

Lecture 3/4

Fast spectroscopy in Supramolecular Chemistry and Nanomaterials

Chapter 11.

and

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

or (same document from different source)

http://home.medewerker.uva.nl/binaries/content/documents/personalpages/w/i/r.m.williams/en/tab-one/tab-one/cpitem%5B38%5D/asset?1355372849366

 

 

Lecture 4/5

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

 

Lecture 6

Nanomaterials for Solar Fuels

Photoactivated catalysts for water oxidation on nanomaterials

http://pubs.acs.org/doi/full/10.1021/ar500386x

http://pubs.acs.org/doi/full/10.1021/ar9002398

http://pubs.acs.org/doi/full/10.1021/acs.chemrev.5b00229

 

video lectures on solar fuels

https://www.youtube.com/watch?v=ChiSHuxC2Ew

https://www.youtube.com/watch?v=dEUIVPu_PpA

 

Timetable

The schedule for this course is published on DataNose.

Contact information

Coordinator

  • dr. R.M. Williams

Staff

  • dr. Tiddo Mooibroek
  • prof. dr. Joost Reek