TY - BOOK
T1 - Photoresponsive Liquid Crystals Based on Dihydroazulene
AU - Petersen, Anne Ugleholdt
PY - 2016
Y1 - 2016
N2 - The main focus of this thesis was a study upon photoresponsive liquid crystalline materials,with a starting point on the photoactive compound dihydroazulene (DHA). It has been shown thatsome DHAs with liquid crystalline properties can be synthesized, having an aliphatic substituent atthe 2-position. Irradiation of such a DHA in the nematic phase gave partial conversion to avinylheptafulvene (VHF), not showing any changes in the mesophase, though a higher alignmentwas obtained when this sample was irradiated in its liquid crystalline state.Photomicrographs of the DHA under crossed polarizers before irradiation, after irradiation and when allowed toclose back to the DHAFor a disubstituted DHAs, with substituents in both the 2- and 7-positions, it was shown thatthese materials were unstable when heated above 100 °C, leading to side reactions, whichcomplicated analysis of the system. When doped into a nematic host material, the conversion fromDHA to VHF upon irradiation did not affect any change in the dielectric anisotropy. However, theorder parameter was strongly affected by the formation of the VHF structure. It was found that thisDHA in a nematic host absorbed light when photons were passed through parallel to the alignmentof the nematic phase, while when the incident angle was perpendicular, the absorbance wasdrastically reduced. These differences for parallel and perpendicular absorbances wereindistinguishable for the VHF form. The corresponding azulene systems were also studied, whichshowed good alignment between the transition dipole moment and the direction of the nematic host,showing that azulene could be a useful dye for doping into liquid crystalline host materials.As esters are a commonly used linking group in liquid crystalline chemistry, it was chosen toinvestigate the physical properties of a series of thioester analogues. Only few examples of liquidcrystalline thioesters have been reported in the literature. It was shown that these materials haveindeed been overlooked in the field of liquid crystal chemistry, as they were found to showinteresting properties.Chiral azulenes were made and showed interesting results when doped into host CB9CB, whichhas been shown to exhibit the lesser understood NTB phase. Mixtures of chiral azulenes in CB9CBupon cooling not only formed the NTB phase with a potential dye molecule present but also resultedin the formation of another nematic phase, which is currently not totally understood.Efforts also went into finishing projects started on in my Master’s project and were initiallyenvisaged as the methodologies for designing DHA molecules with liquid crystal properties. Thisincluded the reaction of adding a triisopropylacetylide to azulenium cation, and a synthesis of alinear “double DHA”. As these projects did not end up being viable strategies for liquid crystallinematerials, they are not included in the thesis but the articles are attached in the appendix.
AB - The main focus of this thesis was a study upon photoresponsive liquid crystalline materials,with a starting point on the photoactive compound dihydroazulene (DHA). It has been shown thatsome DHAs with liquid crystalline properties can be synthesized, having an aliphatic substituent atthe 2-position. Irradiation of such a DHA in the nematic phase gave partial conversion to avinylheptafulvene (VHF), not showing any changes in the mesophase, though a higher alignmentwas obtained when this sample was irradiated in its liquid crystalline state.Photomicrographs of the DHA under crossed polarizers before irradiation, after irradiation and when allowed toclose back to the DHAFor a disubstituted DHAs, with substituents in both the 2- and 7-positions, it was shown thatthese materials were unstable when heated above 100 °C, leading to side reactions, whichcomplicated analysis of the system. When doped into a nematic host material, the conversion fromDHA to VHF upon irradiation did not affect any change in the dielectric anisotropy. However, theorder parameter was strongly affected by the formation of the VHF structure. It was found that thisDHA in a nematic host absorbed light when photons were passed through parallel to the alignmentof the nematic phase, while when the incident angle was perpendicular, the absorbance wasdrastically reduced. These differences for parallel and perpendicular absorbances wereindistinguishable for the VHF form. The corresponding azulene systems were also studied, whichshowed good alignment between the transition dipole moment and the direction of the nematic host,showing that azulene could be a useful dye for doping into liquid crystalline host materials.As esters are a commonly used linking group in liquid crystalline chemistry, it was chosen toinvestigate the physical properties of a series of thioester analogues. Only few examples of liquidcrystalline thioesters have been reported in the literature. It was shown that these materials haveindeed been overlooked in the field of liquid crystal chemistry, as they were found to showinteresting properties.Chiral azulenes were made and showed interesting results when doped into host CB9CB, whichhas been shown to exhibit the lesser understood NTB phase. Mixtures of chiral azulenes in CB9CBupon cooling not only formed the NTB phase with a potential dye molecule present but also resultedin the formation of another nematic phase, which is currently not totally understood.Efforts also went into finishing projects started on in my Master’s project and were initiallyenvisaged as the methodologies for designing DHA molecules with liquid crystal properties. Thisincluded the reaction of adding a triisopropylacetylide to azulenium cation, and a synthesis of alinear “double DHA”. As these projects did not end up being viable strategies for liquid crystallinematerials, they are not included in the thesis but the articles are attached in the appendix.
UR - http://rex.kb.dk/KGL:KGL:KGL01009224303
M3 - Ph.D. thesis
BT - Photoresponsive Liquid Crystals Based on Dihydroazulene
PB - Department of Chemistry, Faculty of Science, University of Copenhagen
ER -