Laboratoire de caractérisation photophysique des matériaux conjugués, Department of Chemistry, Pavillon JA Bombardier, Université de Montréal , CP 6128, succ. Centre-ville, Montreal, Quebec H3C 3J6, Canada.
ACS Appl Mater Interfaces. 2013 Dec 11;5(23):12646-53. doi: 10.1021/am4040009. Epub 2013 Nov 27.
A series of symmetric and unsymmetric conjugated azomethines derived from cinnamaldehyde and 2,5-diaminothiophene-3,4-dicarboxylic acid diethyl ester were prepared. The optical, electrochemical, and spectroelectrochemical properties of the electronic push-pull and push-push triads were investigated. Their properties could be tuned contingent on the cinnamaldehyde's electron withdrawing and donating substituents. The push-push symmetric derivative exhibited positive solvatochromism with the absorbance spanning some 31 nm, depending on the solvent polarity. Solvent dependent spectroelectrochemistry was also found for the symmetric push-push azomethine. The color of the neutral state and radical cation spanned 215 nm. The most pronounced color transition of the purple colored material was found in dimethyl sulfoxide (DMSO), where the color bleached with electrochemical oxidation. This was a result of the absorbance shifting into the near infrared (NIR) and not from decomposition of the azomethine. Electrochromic devices with the azomethines possessing desired reversible oxidation and color changes in the visible were fabricated and tested to demonstrate the applicability of these azomethine triads in devices.
一系列对称和不对称的共轭腙化合物是由肉桂醛和 2,5-二氨基噻吩-3,4-二羧酸二乙酯衍生而来。研究了电子推拉和推拉三联体的光学、电化学和光谱电化学性质。它们的性质可以根据肉桂醛的吸电子和供电子取代基进行调节。对称的推拉对称衍生物表现出正溶剂化变色，吸收范围约为 31nm，取决于溶剂的极性。对于对称的推拉腙，也发现了溶剂依赖性光谱电化学。中性态和自由基阳离子的颜色跨度为 215nm。在二甲基亚砜（DMSO）中，紫色材料的颜色变化最明显，随着电化学氧化，颜色褪色。这是由于吸收峰移到近红外（NIR）区域，而不是腙的分解。制备了具有所需可逆氧化和颜色变化的可见电致变色器件，并对其进行了测试，以证明这些腙三联体在器件中的适用性。
