TY - BOOK

T1 - π-Extended Tetrathiafulvalenes

AU - Petersen, Johannes Fabritius

PY - 2016

Y1 - 2016

N2 - This Ph.D.-thesis focuses on the synthesis and properties of various redox-active¼-extended tetrathiafulvalenes. One class of molecules are so-called H-cruciformshaped molecules. In these molecules the formation of a central stilbene doublebond is elucidated. Here it was found that the formation of the stilbene bond originatesfrom preformation of a 1,3-dioxa-2-phospholane, formed by reaction betweenP(OEt)3 present under the reaction conditions and two aldehydes. Underthe reaction conditions this 1,3-dioxa-2-phospholane can then be converted to thestilbene. These mechanistic studies lead to the improvement of the synthesis of theH-cruciform, making the synthesis reliable and the product easy to purify. A newH-cruciform family with differentially protected acetylenes were also synthesized.These H-Cruciform structures were subsequently employed in polymerization reactionsin the attempt to form2D polymeric sheets with multiple redox sites. Theseexperiments were unfortunately unfruitful. Another class of molecules is based onvarious indenofluorene scaffolds. Here seven new members of this emerging familyof compounds were synthesized and characterized electrochemically. While someof the molecules were found to exhibit extensive aggregation phenomena in theirCVs, the inclusion of steric bulk in some of the systemswere shown to hamper theseaggregation phenomena

AB - This Ph.D.-thesis focuses on the synthesis and properties of various redox-active¼-extended tetrathiafulvalenes. One class of molecules are so-called H-cruciformshaped molecules. In these molecules the formation of a central stilbene doublebond is elucidated. Here it was found that the formation of the stilbene bond originatesfrom preformation of a 1,3-dioxa-2-phospholane, formed by reaction betweenP(OEt)3 present under the reaction conditions and two aldehydes. Underthe reaction conditions this 1,3-dioxa-2-phospholane can then be converted to thestilbene. These mechanistic studies lead to the improvement of the synthesis of theH-cruciform, making the synthesis reliable and the product easy to purify. A newH-cruciform family with differentially protected acetylenes were also synthesized.These H-Cruciform structures were subsequently employed in polymerization reactionsin the attempt to form2D polymeric sheets with multiple redox sites. Theseexperiments were unfortunately unfruitful. Another class of molecules is based onvarious indenofluorene scaffolds. Here seven new members of this emerging familyof compounds were synthesized and characterized electrochemically. While someof the molecules were found to exhibit extensive aggregation phenomena in theirCVs, the inclusion of steric bulk in some of the systemswere shown to hamper theseaggregation phenomena

UR - https://soeg.kb.dk/permalink/45KBDK_KGL/fbp0ps/alma99122427586005763

M3 - Ph.D. thesis

BT - π-Extended Tetrathiafulvalenes

PB - Department of Chemistry, Faculty of Science, University of Copenhagen

ER -