A series of photochromic dithienylethene-containing triarylboranes has been synthesized and characterized. The X-ray crystal structure of (4,5-bis(2,5-dimethylthiophen-3-yl)-thiophen-2-yl)dimesitylborane has been determined. An intense electronic absorption band was observed in all the triarylborane-containing compounds, corresponding to the intramolecular charge-transfer transition from the π-conjugated thiophene / fused thiophene / bithiophene to the vacant pπorbital of boron. This class of compounds was also found to bind fluoride ion such that the trigonal planar geometry of the boron center would be changed to tetrahedral, leading to a significant perturbation in the photophysical properties. Upon photo-excitation into the transition band, (4,5-bis(2,5-dimethylthiophen-3-yl)-thiophen-2-yl)dimesityl- borane and (4,5-bis-(2,5-dimethylthiophen-3-yl)-thieno[3,2-b]thiophen-2-yl)- dimesitylborane displayed multi-addressable photochromic reactivities upon addition of fluoride, in which a green solution was found in the closed form of the unbound compounds, while they changed to a purple color upon fluoride binding. Interestingly, both (4',5'-bis(2,5-dimethyl-thiophen-3-yl)-2,2'- bithiophen-5-yl)dimesitylborane and (4',5'-bis(2,5-dimethyl-thiophen-3-yl)-2,2'- bithiophen-3-yl)dimesitylborane displayed gated photochromic reactivities upon addition of fluoride, while only typical photochromic reactivity was observed in (4',5'-bis(2,5-dimethyl-thiophen-3-yl)-2,2'-bithiophen-4-yl)- dimesitylborane, indicative of a strong influence of the substituent effect on the photochromic reactivity upon incorporation of the -BMes2 group. A series of photochromic dithienylethene-containing β-diketones and the corresponding boron(III) compounds, appended with -BF2, -B(C6F5)2 and -BPh2, have been designed and synthesized. Upon photo-excitation into the transition band, typical photochromism was observed in all the dithienylethene- containing β-diketone ligands with the color changed from pale yellow to green in degassed benzene solution. Upon incorporation of the -BF2 and -B(C6F5)2 groups, near-infrared responsive photochromic behavior was observed, in which the absorption of the closed form was found to be at ca. 758-863 nm, suggesting that a pronounced perturbation of the dithienylethene was achieved by coordination of the boron(III) center. Moreover, a significant reduction in luminescence intensity of over 90 % was observed upon photocyclization, indicative of their potential application as photoswitchable luminescence materials. The thermal stability of the closed form and the activation energy for the thermal cycloreversion have also been studied on the representative compounds, 1-(4,5-bis(2,5-dimethylthiophen-3-yl)thiophen-2- yl)-butane-1,3-dione and difluoroboryl(1-(4,5-bis(2,5-dimethylthiophen-3-yl)- thiophen-2-yl)butane-1,3-dionate). A series of photochromic dithienylethene-containing BODIPY has been successfully prepared and characterized. The electronic absorption properties have been studied. These compounds showed an intense visible absorption band, corresponding to the 0-0 band of a strong S0→S1 transition of the BODIPY core, with a weak and broad absorption band at higher energy, corresponding to the S0→ S2 transition of the BODIPY core. An absorption band in the UV region was also observed in 2,3-bis(2,5-dimethyl- thiophen-3-yl)thiophene-containing derivatives, corresponding to the π→π* transitions of the dithienylethene moiety. The photochromic reactivities have also been studied such that the photostationary state was found to be reached upon irradiation in the UV region for over eight hours, while no observable changes would be obtained upon photo-excitation in the visible region. The slow conversion rate has been suggested to be attributed to the fact that a rapid excitation energy transfer could occur from the excited Th-DTE to the BODIPY moiety, rendering the suppression of the photocyclization. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Photochromism is a phenomenon where two isomers with markedly different absorption spectra are interconverted by a reversible photochemical reaction. The photochromism of 1’,3’,3’-trimethyl-6-nitrospiro[2H-1]-benzopyran-2,2’-indoline (NSP) and 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene) (DAE) was studied in aqueous solutions containing NaCl and the bile salts sodium cholate (NaC), sodium deoxycholate (NaDC) or sodium taurocholate (NaTC). Bile salts are amphiphilic compounds that aggregate in water. These aggregates can solubilize hydrophobic organic compounds in water and affect the reactivity of the bound compounds. NSP and DAE are photochromic compounds that can be switched between a colored and a colorless isomer. The colored isomer of DAE can only be transformed into the colorless form by irradiation of light, while the colored isomer of NSP is also converted into the colorless form by a dark reaction. The dark reaction rate constant of NSP increases at high concentrations of bile salt and NaCl. The bile salt structure also affects the dark reaction rate constant, which is smaller in NaTC and approximately the same in NaC and NaDC. The activation energy for the reaction in all conditions studied is similar to the value reported for polar organic solvents. A method that employs HPLC was developed to determine the molar absorptivity coefficients of photochromic compounds. The values obtained were important to determine the quantum yields for photocoloration (ΦAB) and photodecoloration (ΦBA). Quantum yield values were determined by a photokinetic method that employs irradiation at a single wavelength and numerical analysis. The values of ΦAB and ΦBA for DAE in bile salts are the same as the values in cyclohexane. For NSP, ΦAB is dependent on the structure of the bile salt and increases in the order NaTC < NaC < NaDC. / Graduate

Photochromism is a phenomenon where two isomers with markedly different absorption spectra are interconverted by a reversible photochemical reaction. The photochromism of 1,3,3-trimethyl-6-nitrospiro[2H-1]-benzopyran-2,2-indoline (NSP) and 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene) (DAE) was studied in aqueous solutions containing NaCl and the bile salts sodium cholate (NaC), sodium deoxycholate (NaDC) or sodium taurocholate (NaTC). Bile salts are amphiphilic compounds that aggregate in water. These aggregates can solubilize hydrophobic organic compounds in water and affect the reactivity of the bound compounds. NSP and DAE are photochromic compounds that can be switched between a colored and a colorless isomer. The colored isomer of DAE can only be transformed into the colorless form by irradiation of light, while the colored isomer of NSP is also converted into the colorless form by a dark reaction. The dark reaction rate constant of NSP increases at high concentrations of bile salt and NaCl. The bile salt structure also affects the dark reaction rate constant, which is smaller in NaTC and approximately the same in NaC and NaDC. The activation energy for the reaction in all conditions studied is similar to the value reported for polar organic solvents. A method that employs HPLC was developed to determine the molar absorptivity coefficients of photochromic compounds. The values obtained were important to determine the quantum yields for photocoloration (AB) and photodecoloration (BA). Quantum yield values were determined by a photokinetic method that employs irradiation at a single wavelength and numerical analysis. The values of AB and BA for DAE in bile salts are the same as the values in cyclohexane. For NSP, AB is dependent on the structure of the bile salt and increases in the order NaTC < NaC < NaDC. / Graduate / 2015-03-31

Thesis (M.S.) -- Worcester Polytechnic Institute. / Keywords: photochromic; spirooxazine; Ormosil Includes bibliographical references (p.52-54).

Thesis (Ph.D.)--University of Hong Kong, 2003. / Also available in print.

No description available.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Une série de bisthiényléthènes (BTE), chromophores photochromes, à différents ponts éthène centraux a été synthétisée. Jusque là, la conception rationnelle des BTE a reposé sur la nature des substituants des groupes latéraux. Dans notre travail, nous avons étudié l'influence de l'aromaticité du pont sur les propriétés photochromes. De plus, alors que les cycles à cinq atomes sont le plus souvent utilisés, nous avons introduit des cycles à six atomes au niveau de ce pont. Dans le Chapitre 1, les définitions principales liées au photochromisme, ainsi que des exemples, sont donnés. Le Chapitre 2 est dédié au BTTE, un BTE à pont benzobisthiadiazole, doté d'excellentes propriétés photochromes. Sa fluorescence peut être modulée par solvato- et photochromisme. c-BTTE, l'isomère fermé, a une excellente stabilité dans divers solvants et à l'état solide. Il ne présente pas de retour thermique typique des BTE à pont cyclique à six atomes. Le Chapitre 3 est consacré à des composés comportant des ponts de divers degrés d'aromaticité (BTE-NA, BTA et BTTA). Leur fluorescence peut être modulée par solvato- et photochromisme. Une faible aromaticité peut être corrélée à une irréversibilité thermique, comme illustré par le cas du BTTA à pont benzobisthiadiazole. De plus, la faible barrière énergétique entre les conformations parallèle et anti-parallèle et la grande différence d'absorption entre isomères conduisent à une conversion totale de BTTA à c-BTTA. Des molécules à pont benzothiadiazole, conçues pour la complexation et la commutation de propriétés optiques non linéaires, ont été obtenues (Chapitres 4 et 5). Cependant, pour l'instant, les propriétés visées n'ont pas été mises en évidence. / A series of photochromic bisthienylethenes (BTE) chromophores with different central ethene bridges were synthesized. Up to date, the rational design of BTE have been mainly carried out on the side aryl groups. In our work, the influence of the aromaticity of the central ethene bridge on the photochromic properties was studied. Moreover, unlike in the literature where most of BTE have a five-membered ring bridge, six-membered ring bridges were used. In Chapter 1, examples of photochromes are given, along with the main definitions. Chapter 2 deals with BTTE, a BTE with a benzobisthiadiazole bridge and with excellent photochromic properties. c-BTTE, the closed isomer, exhibits excellent thermal stability in various solvents and in the solid state. Its fluorescence can be modulated by solvato- and photochromism. It eliminates the usual bias of thermal back reaction, typical of BTE with a six-membered ring ethene bridge. Chapter 3 is devoted to compounds with bridges having different aromaticities (BTE-NA, BTA and BTTA). Their fluorescence can be modulated by solvato- and photochromism. The relation between aromaticity and thermal stability was established: the low aromaticity of the central ethene bridge with benzobisthiadiazole unit leads to a thermal irreversibility for BTTA, and the small energy barrier between the parallel and anti-parallel conformers and the great difference in absorption between BTTA and c-BTTA allow the full conversion from BTTA to c-BTTA. Molecules with a benzothiadiazole bridge, designed for complexation and for switchable nonlinear optical properties were prepared (Chapters 4 and 5). However, the targeted properties were not evidenced up to now.

Este trabalho teve por objetivo o preparo e estudo das propriedades de vidros fotocrômicos. Foram preparados vidros de aluminoborosilicatos de potássio (40\'SI\'\'O IND. 2\'.10\'AL IND. 2\'\'O IND. 3\'.(50-x)\'B IND. 2\'\'O IND. 3\'.X\'K IND. 2\'\'O\'- 14,9 < x < 17,7) dopados com \'AG\'\'CL\' e \'CU POT. 2+\'. As amostras foram fundidas em cadinho de platina, em forno de elementos resistivos de \'SI\'\'C\', a \'1400 GRAUS\'C por duas horas, sendo derramados sobre molde de aço inoxidável. Uma tentativa de análise química quantitativa dos componentes após a fusão foi feita por Retroespalhamento de Rutherford. A proporção de prata retida no vidro foi determinada por este método. Medidas de dilatometria e densidade foram feitas para amostras de composição base diferentes. As medidas de dilatometria permitem a obtenção do coeficiente de dilatação térmica, e os parâmetros típicos de vidros conhecidos como: temperatura de transição vítrea e temperatura de \"softening dilatométrico\". Tratamentos térmicos em temperaturas próximas do ponto de amolecimento (softening point) provocam a precipitação de partículas coloidais de \'AG\'\'CL\' na matriz vítrea. Estas são responsáveis pelo comportamento fotocrômico dos vidros. Fatias de uma amostra foram submetidas a programas de tratamento térmico de 0,5 h a várias temperaturas entre \'480 GRAUS\'C e \'620 GRAUS\'C e programas de vários intervalos de tempo entre 0,25 e 1,25h a \'600 GRAUS\'C. As propriedades de absorção óptica das várias fatias, antes e depois de exposição à luz UV, foram comparadas. As características morfológicas das partículas coloidais de \'AG\'\'CL\' produzidas pelos tratamentos térmicos foram investigadas por SAXS. Os raios R das partículas mostraram uma relação linear com a temperatura para tratamentos de 0,5 h entre 550 e \'620 GRAUS\'C e uma relação linear de \'R POT. 3\' com o tempo de tratamento a \'600 GRAUS\'C. Duas séries de amostras foram preparadas para estudar: 1. a influência da quantidade de cobre 2. a influência da proporção de \'K IND. 2\'\'O\' em relação a \'B IND. 2\'\'O IND. 3\'. As propriedades de absorção óptica (antes e depois de exposição à luz UV) das amostras das duas séries, submetidas a tratamentos térmicos a \'600 GRAUS\'C por diversos tempos entre 0,25 e 1,6 h foram comparadas. / The purpose of the present work was to prepare and study the properties of photochromic glasses. Potassium aluminoborosilicate glasses (40\'SI\'\'O IND. 2\'.10\'AL IND. 2\'\'O IND. 3\'.(50-x)\'B IND. 2\'\'O IND. 3\'.X\'K IND. 2\'\'O\'- 14,9 < x < 17,7) doped with \'AG\'\'CL\' and \'CU POT. 2+\' were prepared. The samples were melted in platinum crucible, in electric furnace with silicon carbide resistences, at \'1400 GRAUS\'C for two hours, and poured on stainless steel mold. An attempt to perform a quantitative chemical analisis of the components after melting was carried out by Rutherford Backscattering method. The amount of silver incorporated into the glass was determined by this method. Measurements of dilatometry and density were performed for samples of different base composition. The dilatometric measurements give the thermal expansion coefficient, and the typical glass parameters such as glass transition point and dilatometric softening point. Thermal treatments at temperatures near the softening point precipitate colloidal \'AG\'\'CL\' particles in the glass matrix. These particles are responsible for the photochromic characteristics of the glass. Slices of a sample were submitted to thermal treatments for 0.5 hours at temperatures between 480 and \'620 GRAUS\'C and treatments at \'600 GRAUS\'C for several) time intervals between 0.25 and 1.25 hours. The optical absorption properties of these slices, before and after UV light exposure, were compared. The morphological aspects of the \'AG\'\'CL\' coloidal particles were investigated by SAXS. The particle radii R presented a linear relation with the temperature for treatments for 0.5 hour at temperatures between 550 and \'620 GRAUS\'C and a linear relation of \'R POT. 3\' with time for treatments at \'600 GRAUS\'C. Two sample series were prepared to investigate: 1. the influence of the amount of copper 2. the influence of the amount of \'K IND. 2\'\'O\' in relation to the amout of \'B IND. 2\'\'O IND. 3\' The optical absorbances (before and after exposure to UV light) for samples of the two series, annealed at \'600 GRAUS\'C for different times between 0.25 and 1.6 hours were compared.