TY - BOOK
T1 - Light-Harvesting System Based on Subphthalocyanines
AU - Gotfredsen, Henrik
PY - 2018
Y1 - 2018
N2 - This thesis describes the synthesis, characterization, and study of selected subphthalocyanine-based light-harvesting systems. Subphthalocyanines (subpcs) are strongly light-absorbing curved aromatic compounds, being contracted homologs of the well-known phthalocyanine family. A methodology has been developed, allowing for the axial functionalization of subphthalocyanine chloride (subpc-cl) with trimethylsilyl-protected acetylenes in the presence of aluminum chloride. This reaction was used to synthesize several axially alkynylated subpc derivatives. A donoracceptor- functionalized subpc carboxylic acid was synthesized and used as sensitizer in liquid- and solid-state dye-sensitized solar cells (dsscs). Measurements on the solid-state cells yielded the highest reported power conversion efficiency for a subpc-based dssc. Thieno-fused subpcanalogs having one and two 2,5-dichlorothiophene units incorporated instead of benzenes have been synthesized and shown to exhibit comparable broader absorption, lower fluorescence quantum yields, and decreasing aromaticity with increasing number of thiophene units. Fullerene complexation has been studied with a novel subpc-dimer or tweezer and a subpc monomer. Binding studies by 1h-nmr spectroscopy revealed the necessity of preorganization as present in the dimer but absent in the monomer. With the aim of studying intramolecular sensitized singlet fission (sf), a series of subpc-pentacene conjugates was synthesized containing one or multiple (two or four) subpc units in close proximity to one active sf center. The photophysical properties of this series of molecules are currently under investigation by collaborators.
AB - This thesis describes the synthesis, characterization, and study of selected subphthalocyanine-based light-harvesting systems. Subphthalocyanines (subpcs) are strongly light-absorbing curved aromatic compounds, being contracted homologs of the well-known phthalocyanine family. A methodology has been developed, allowing for the axial functionalization of subphthalocyanine chloride (subpc-cl) with trimethylsilyl-protected acetylenes in the presence of aluminum chloride. This reaction was used to synthesize several axially alkynylated subpc derivatives. A donoracceptor- functionalized subpc carboxylic acid was synthesized and used as sensitizer in liquid- and solid-state dye-sensitized solar cells (dsscs). Measurements on the solid-state cells yielded the highest reported power conversion efficiency for a subpc-based dssc. Thieno-fused subpcanalogs having one and two 2,5-dichlorothiophene units incorporated instead of benzenes have been synthesized and shown to exhibit comparable broader absorption, lower fluorescence quantum yields, and decreasing aromaticity with increasing number of thiophene units. Fullerene complexation has been studied with a novel subpc-dimer or tweezer and a subpc monomer. Binding studies by 1h-nmr spectroscopy revealed the necessity of preorganization as present in the dimer but absent in the monomer. With the aim of studying intramolecular sensitized singlet fission (sf), a series of subpc-pentacene conjugates was synthesized containing one or multiple (two or four) subpc units in close proximity to one active sf center. The photophysical properties of this series of molecules are currently under investigation by collaborators.
UR - https://rex.kb.dk/primo-explore/fulldisplay?docid=KGL01011959768&context=L&vid=NUI&search_scope=KGL&tab=default_tab&lang=da_DK
M3 - Ph.D. thesis
BT - Light-Harvesting System Based on Subphthalocyanines
PB - Department of Chemistry, Faculty of Science, University of Copenhagen
ER -