Sampson Kathleen L, Jiang Xiaoqin, Bukuroshi Esmeralda, Dovijarski Aleksa, Raboui Hasan, Bender Timothy P, Kasdish Karl M
Department of Chemical Engineering and Applied Chemistry , University of Toronto , 200 College Street , Toronto , Ontario , Canada M5S 3E4.
Department of Chemistry , University of Houston , Houston , Texas 77204-5003 , United States.
J Phys Chem A. 2018 May 10;122(18):4414-4424. doi: 10.1021/acs.jpca.8b02023. Epub 2018 Apr 26.
An extensive study of the electrochemical and spectroelectrochemical properties of 14 boron subphthalocyanine (BsubPc) derivatives with various axial and peripheral substituents was performed in 1,2-dichloromethane (CHCl) containing 0.1 M tetra- n-butyl-ammonium perchlorate (TBAP) as the supporting electrolyte. From the cyclic voltammetry results, all compounds exhibit one oxidation and at least two reduction processes within the solvent potential window of +1.6 to -1.8 V vs SCE. It was found that the reversibility of the redox reactions depends on the axial and peripheral substituents and the dipole moment of the boron-to-axial substituent. In general, UV-vis absorption spectra of the singly reduced BsubPc derivatives exhibit three equal intensity peaks in the 450 to 650 nm region that are derived from the maximum BsubPc absorbance peak upon reduction. Axial substituents affect the intensity of the three peaks upon reduction, while peripheral substituents shift the position of the peaks to higher wavelengths. Upon oxidation, the UV-vis absorption profile flattens considerably with only a single broad (∼300 nm) band apparent. Understanding the effect of substituents on the stability of the redox processes of BsubPcs will aid in further development of these materials for applications in organic electronic devices.
对14种带有不同轴向和周边取代基的硼代亚酞菁（BsubPc）衍生物在含有0.1 M四丁基高氯酸铵（TBAP）作为支持电解质的1,2 - 二氯甲烷（CHCl）中进行了电化学和光谱电化学性质的广泛研究。从循环伏安法结果来看，所有化合物在相对于饱和甘汞电极（SCE）为 +1.6至 -1.8 V的溶剂电位窗口内都呈现出一个氧化过程和至少两个还原过程。研究发现，氧化还原反应的可逆性取决于轴向和周边取代基以及硼与轴向取代基之间的偶极矩。一般来说，单还原的BsubPc衍生物的紫外 - 可见吸收光谱在450至650 nm区域呈现出三个强度相等的峰，这些峰源自还原时BsubPc的最大吸收峰。轴向取代基会影响还原时这三个峰的强度，而周边取代基则会使峰的位置向更高波长移动。氧化时，紫外 - 可见吸收曲线会大幅变平，仅出现一个明显的宽（约300 nm）带。了解取代基对BsubPcs氧化还原过程稳定性的影响将有助于进一步开发这些材料用于有机电子器件。
