Stuttgart, Universiẗat, Diss., 2000. / Dateiformat: tgz, Dateien im PDF-Format.

Stuttgart, Universiẗat, Diss., 2000 (Nicht für den Austausch).

The fulgide and fulgimide family constitutes an important class of organic photochromic compounds. The ability of fulgides and fulgimides to interconvert between two key forms by irradiation of different wavelength of light has made them promising material in optical memory devices, optical switches and sensors, and specialty dyes and inks. Thermal stability and hydrolytic stability of fulgides and fulgimides are essential for their practical applications. A deuterated trifluoromethyl indolylfulgide was synthesized based on the synthetic pathway of the proteo trifluoromethyl indolylfulgide using commercially available deuterated starting materials. Deuteration of the isopropylidene group improved the thermal stability of the indolylfulgide by a factor of 7. Fulgimides are the most important fulgide derivatives. Fulgimides improve the hydrolytic stability of fulgides by replacing the succinic anhydride ring with a succinimide ring. A novel trifluoromethyl N-ethoxycarbonylmethyl indolylfulgimide was synthesized from trifluoromethyl indolylfulgide. The trifluoromethyl indolylfulgide was synthesized on a large scale in five steps with an overall yield of 18%. The indolylfulgide was then converted to indolylfulgimide by aminolysis follow by dehydration. The N-ethoxycarbonylmethyl indolylfulgimide showed enhanced hydrolytic stability and photochemical stability in 70/30 ethanol/water. Three novel aqueous soluble fulgimides, trifluoromethyl carboxylic acid indolylfulgimide, dicarboxylic acid indolylfulgimide, and H-carboxylic acid indolylfulgimide, were synthesized. In sodium phosphate buffer (pH 7.4) at 37 ºC, an unusual hydrolysis of the trifluoromethyl group of the closed form of the carboxylic acid indolylfulgimide resulted in the dicarboxylic acid indolylfulgimide which has an additional carboxylic acid group. The closed form of dicarboxylic acid indolylfulgimide was further decarboxylated to generate H-carboxylic acid indolylfulgimide which was not photochromic. The trifluoromethyl dicarboxylic acid indolylfulgimide is the most robust fulgimide yet reported in aqueous solution. A novel aqueous soluble methyl carboxylic acid indolylfulgimide was synthesized from methyl indolylfulgide. The methyl indolylfulgide was synthesized in five steps with an overall yield of 21%. The methyl carboxylic acid indolylfulgimide was synthesized by aminolysis follow by dehydration. The methyl carboxylic acid indolylfulgimide is expected to have improved thermal and photochemical stability in aqueous solutions relative to the trifluoromethyl analog.

The goal of this thesis is to design both liquid crystal hosts and photochromic dopants terminated with short siloxane oligomers in order to produce homogeneous liquid crystal mixtures containing a photochromic component for liquid crystal photoswitches. Some of the liquid crystals terminated with short siloxane oligomers were also found to form 'de Vries'-type SmA phases, which minimize the formation of chevrons and zigzag defects that severely degrade the quality of electro-optic devices. In the first part of the thesis, siloxane-terminated phenylpyrimidine liquid crystals were synthesized and characterized. They form SmC phases and, in some cases, SmA phases. Addition of a terminal halogen substituent on the alkoxy side-chain broadens the SmA temperature range. It was shown that combining a structural element that promotes the formation of a SmC phase with one that promotes the formation of a SmA phase in a mesogen with a 2-phenylpyrimidine core results in a maximum layer contraction of 1.6% for 2-(4-(11-(1,1,1,3,3,5,5-heptamethyltrisiloxanyl)undecyloxy)phenyl)-5-(1-chlorooctyloxy)pyrimidine (33a), which may be considered a ‘de Vries’ material. As an extension of the result obtained in the first project, siloxane-terminated biphenyl benzoate and phenyl benzoate liquid crystals were synthesized and their phase behavior studied. They form SmC phases and, in some cases, SmA and SmI phases. Addition of a terminal chloro substituent on alkoxy side-chain results in a broader SmA temperature range and, in some cases, also affects the nature of the mesophase formed. The compound 4-[6-(1,1,1,3,3,5,5-heptamethyltrisiloxanyl)hexanoyloxy]phenyl 4-(8-chlorooctyloxy)benzoate (40b) is characterized by a maximum layer shrinkage of only 1.7%, which may be considered to possess some ‘de Vries’ character. Finally, siloxane-terminated fulgide derivatives were designed as photochromic dopants for liquid crystal photoswitches. Compound 41 was designed and synthesized and proved to be an oil at room temperature. Solid fulgide precusors 42, 43a and 44b were then assessed as photochromic dopants in terms of fast switching and high quantum yield requirements of a photoswitch, and their photophysical properties were studied in solution. The isomer composition at the photostationary state suggests that the competition from E-Z isomerization is likely too high for compounds 42, 43a and 44b to be suitable as photochromic dopants for photoswitches. / Thesis (Ph.D, Chemistry) -- Queen's University, 2009-05-28 12:46:13.992

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Stuttgart, Univ., Diss., 2000.