Abstract
This Ph.D.-thesis focuses on the synthesis and properties of various redox-active
¼-extended tetrathiafulvalenes. One class of molecules are so-called H-cruciform
shaped molecules. In these molecules the formation of a central stilbene double
bond is elucidated. Here it was found that the formation of the stilbene bond originates
from preformation of a 1,3-dioxa-2-phospholane, formed by reaction between
P(OEt)3 present under the reaction conditions and two aldehydes. Under
the reaction conditions this 1,3-dioxa-2-phospholane can then be converted to the
stilbene. These mechanistic studies lead to the improvement of the synthesis of the
H-cruciform, making the synthesis reliable and the product easy to purify. A new
H-cruciform family with differentially protected acetylenes were also synthesized.
These H-Cruciform structures were subsequently employed in polymerization reactions
in the attempt to form2D polymeric sheets with multiple redox sites. These
experiments were unfortunately unfruitful. Another class of molecules is based on
various indenofluorene scaffolds. Here seven new members of this emerging family
of compounds were synthesized and characterized electrochemically. While some
of the molecules were found to exhibit extensive aggregation phenomena in their
CVs, the inclusion of steric bulk in some of the systemswere shown to hamper these
aggregation phenomena
¼-extended tetrathiafulvalenes. One class of molecules are so-called H-cruciform
shaped molecules. In these molecules the formation of a central stilbene double
bond is elucidated. Here it was found that the formation of the stilbene bond originates
from preformation of a 1,3-dioxa-2-phospholane, formed by reaction between
P(OEt)3 present under the reaction conditions and two aldehydes. Under
the reaction conditions this 1,3-dioxa-2-phospholane can then be converted to the
stilbene. These mechanistic studies lead to the improvement of the synthesis of the
H-cruciform, making the synthesis reliable and the product easy to purify. A new
H-cruciform family with differentially protected acetylenes were also synthesized.
These H-Cruciform structures were subsequently employed in polymerization reactions
in the attempt to form2D polymeric sheets with multiple redox sites. These
experiments were unfortunately unfruitful. Another class of molecules is based on
various indenofluorene scaffolds. Here seven new members of this emerging family
of compounds were synthesized and characterized electrochemically. While some
of the molecules were found to exhibit extensive aggregation phenomena in their
CVs, the inclusion of steric bulk in some of the systemswere shown to hamper these
aggregation phenomena
| Original language | English |
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| Publisher | Department of Chemistry, Faculty of Science, University of Copenhagen |
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| Publication status | Published - 2016 |