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  4. Boron-Nitrogen Dative Bonds in Structural Supramolecular Chemistry
 
doctoral thesis

Boron-Nitrogen Dative Bonds in Structural Supramolecular Chemistry

Sheepwash, Erin  
2012

This work describes the use of boron-nitrogen dative bonds in supramolecular chemistry. Molecular tectons have been synthesized for crystal engineering. These tectons are linked via B-N dative bonds to form 1-dimensional polymers and macrocycles. B-N dative bonds were further used for the formation of crystalline organic networks by assembly of a tritopic boronate ester with ditopic N-donor ligands. These networks could be structurally characterized by single crystal X-ray diffraction to reveal 2-dimensional polymers. These structures were observed by PXRD to collapse upon removal of solvent. The reaction of a larger triboronate ester with 4,4'-bipyridine resulted in an organogel which formed with as little as 0.5 wt% of the network in toluene. The orange gel exhibited thermochromic properties, with a Tgel of 60 °C. Association constants for the formation of B-N dative bonds between dioxaborole and pyridyl ligands were examined by 1H NMR and ITC titrations. Ka values in excess of 106 M-1 can be obtained by varying the electronics of the reaction partners. The adducts have been characterized comprehensively by single crystal X-ray diffraction. Finally, the dative B-N bond was used for the synthesis of main-chain supramolecular polymers. Self-complementary monomers were synthesized containing a dialkylaminopyridine and a dioxaborole. These monomers assembled in chloroform to form polymers which were characterized by viscosity and DOSY NMR experiments.

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Type
doctoral thesis
DOI
10.5075/epfl-thesis-5391
Author(s)
Sheepwash, Erin  
Advisors
Severin, Kay  
Date Issued

2012

Publisher

EPFL

Publisher place

Lausanne

Thesis number

5391

Total of pages

160

Subjects

Boronic acids

•

Crystal engineering

•

Networks

•

Dative bonds

•

Supramolecular polymers

•

Acides boroniques

•

Ingénierie cristalline

•

Réseaux

•

Liaisons datives

•

Polymères supramoleculaires

EPFL units
LCS  
Faculty
SB  
School
ISIC  
Doctoral School
EDCH  
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/81859
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