Repository logo

Infoscience

  • English
  • French
Log In
Logo EPFL, École polytechnique fédérale de Lausanne

Infoscience

  • English
  • French
Log In
  1. Home
  2. Academic and Research Output
  3. EPFL thesis
  4. Multicomponent Assembly of Boronic Acid-Based Macrocycles, Cages, and Polymers
 
doctoral thesis

Multicomponent Assembly of Boronic Acid-Based Macrocycles, Cages, and Polymers

Içli, Burçak  
2012

This work describes the synthesis and characterization of boronic acid-based supramolecular structures. Different reversible interactions such as boronate ester formation, imine condensation and dative B–N bond formation are used to assemble macrocycles, cages and polymers. Multicomponent condensation reactions of different diamines with tetraols and formylphenylboronic acids give macrocycles via formation of imine bonds and boronate esters. The [4+2+2] condensation products are generally preferred but larger macrocycles are observed for some combinations of staring materials. The larger macrocycles are in dynamic equilibrium with the smaller [4+2+2] products. Utilization of a triamine instead of the diamine results in the formation of molecular cages. The syntheses of these cages require the formation of 18 covalent bonds between 11 building blocks, and, interestingly, can be performed in a ball mill. Multicomponent reactions of diboronic acids, catechol derivatives, and different pyridyl ligands are described. The condensation of diboronic acids with catechols gives dioxaboroles. Upon crystallization, the ester aggregates with the N-donor ligands via dative B−N bonds. Depending on the nature of the pyridyl ligand, molecularly defined macrocycles, cages or polymeric structures are obtained. One-dimensional polymers are formed with 4,4-bipyridine and 1,2-di(4-pyridyl)ethylene, whereas a two-dimensional network is obtained with the tetradentate ligand tetra(4-pyridylphenyl)ethylene. A tripyridyl linker results in the formation trigonal prismatic cages. The size of the cages can be varied by changing the diboronic acid building block. The cages are able to encapsulate polyaromatic molecules such as triphenylene or coronene. The results highlight the potential of dative B−N bonds in structural supramolecular chemistry and crystal engineering.

  • Files
  • Details
  • Metrics
Loading...
Thumbnail Image
Name

EPFL_TH5528.pdf

Access type

restricted

Size

16.68 MB

Format

Adobe PDF

Checksum (MD5)

a95b810115d874b2810a929b5150c75c

Logo EPFL, École polytechnique fédérale de Lausanne
  • Contact
  • infoscience@epfl.ch

  • Follow us on Facebook
  • Follow us on Instagram
  • Follow us on LinkedIn
  • Follow us on X
  • Follow us on Youtube
AccessibilityLegal noticePrivacy policyCookie settingsEnd User AgreementGet helpFeedback

Infoscience is a service managed and provided by the Library and IT Services of EPFL. © EPFL, tous droits réservés