The synthesis of five quinolines 8-octyloxy-4-[4-(octyloxy)phenyl]quinoline and 6-alkoxy- 2-(4-alkoxyphenyl)-4-[(4-octyloxy)aryl]quinolines are described by three-component coupling reaction mediated by Lewis acid FeCl3 and Yb(OTf)3. 4-n-octyloxybenzaldehyde, anisaldehyde, 4-n-octyloxyaniline p-anisidine, and 1-ethynyl-4-heptyloxybenzene, 1-ethynyl-4-octyloxybenzene and 2-ethynyl-6-heptyloxynaphthalene are the reagents in this protocol. A Yb3+ catalyst resulted in higher yields of quinolines than Fe3+. Polarizing optical microscopy (POM) revealed that none of the quinolines were liquid crystals, even the more anisotropic. UV-Vis measurements of one of the quinolines in polar solvent show two absorption bands at 280 and 350 nm related to π,π* and n,π* transitions. No changes were observed to lower-energy absorption band (ε < 104 mol L-1 cm-1) related to n,π* transition. A laser flash photolysis study for one of the quinolines relates a main transient band at 450 nm with a lifetime of 2.6 µs in ethanol, which is completely quenched in the presence of oxygen. This transient band was assigned to triplet-triplet absorption of one of the quinolines, which is semi-oxidised in the presence of phenol. Radiative rate constants have been determined along singlet and triplet excited state energies (3.39 and 3.10 eV, respectively). The chemical structure of one of the quinolines was also unequivocally confirmed by single-crystal X-ray analysis.

As propriedades fotoeletroquímicas dos tertiofenos alcóxi substituídos poli(4,4"dimetóxi-3'-metil-2,2':5',2" tertiofeno) (PDM) e poli(4,4"dipentóxi-3'-metil-2,2':5',2" tertiofeno) (PDP) foram investigadas em termos da influência causada pelo comprimento da cadeia lateral. Experimentos de voltametria cíclica e espectroscopia UV-Vis sugeriram que a temperatura de síntese afeta de modo diferenciado a organização molecular dos materiais e, desse modo, não deve ser usada como regra geral. A maior eficiência de conversão apresentada pelo PDM resulta de seu melhor empacotamento molecular tipo-π. Devido à sua cadeia lateral curta o PDM apresenta uma grande interação entre cadeias, a qual favorece o movimento eletrônico e a condutividade do polímero.

The photoelectrochemical properties of the alkoxy-substituted terthiophenes poly(4,4"dimethoxy-3'-methyl-2,2':5',2" terthiophene) (PDM) and poly(4,4"dipentoxy-3'-methyl-2,2':5',2" terthiophene) (PDP) have been investigated in terms of the influence of side chain length. Cyclic voltammetry and UV-Vis experiments have suggested that the synthesis temperature affects the molecular organization in different ways and, thus it should not be used as a general rule. The more efficient light harvesting of PDM, results from its improved molecular π-stacking. Due to its short side chain, PDM presents a large chain interaction, which favors electron hopping and the polymer conductivity.

Este trabalho descreve o estudo das propriedades eletroquímicas, espectroeletroquímicas e eletrocrômicas de filmes finos de poli(4,4" dimetoxi 3'-metil 2,2':5',2" tertiofeno). A voltametria cíclica in situ foi usada para estudar o efeito da temperatura sobre a eletropolimerização. As temperaturas utilizadas na deposição eletroquímica foram -10, 0, 10, 20 e 40 ºC. Os resultados indicaram que a temperatura de eletropolimerização afeta diretamente o grau de ordenamento molecular do polímero. O tempo de resposta eletrocrômico foi de 0,8 s para clareamento e 0,3 s para escurecimento (para filmes sintetizados a 40 ºC, espessura de 60 nm). Após 1400 ciclos eletrocrômicos, o contraste óptico a 570 nm diminuiu de 31 para 14%. A eficiência eletrocrômica foi intensificada em função do número de ciclos eletrocrômicos. Este fato foi provavelmente causado pela diminuição da carga injetada, necessária para a mudança de cor, sugerindo que as perdas na eletroatividade estão associadas a sítios que não são responsáveis pela mudança de coloração.

This work describes the electrochemical, spectroelectrochemical and electrochromic properties of poly(4,4" dimethoxy 3'-methyl 2,2':5',2" terthiophene) thin films. The effect of temperature on the electropolymerization was studied by cyclic voltammetry measured in situ. The temperatures used were -10, 0, 10, 20, and 40 ºC. Results indicate that the electropolymerization temperature directly affect the degree of chain organization. The optical response time for bleaching was 0.8 s and for coloring 0.3 s (for films synthesized at 40 ºC, 60 nm thick). After 1400 electrochromic cycles, the chromatic contrast at 570 nm changes from 31 to 14%. The coloration efficiency was enhanced as a function of redox cycling. This was probably caused by a decrease in the injected charge necessary for the color change, suggesting that the electroactive losses occurring during the cycles are related to sites not responsible for electrochromic contrast.