Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721, USA.
Langmuir. 2011 Dec 20;27(24):14900-9. doi: 10.1021/la203126c. Epub 2011 Nov 23.
Metalated and free-base A(3)B-type asymmetric phthalocyanines (Pcs) bearing, in the asymmetric quadrant, a flexible alkyl linker of varying chain lengths terminating in a phosphonic acid (PA) group have been synthesized. Two parallel series of asymmetric Pc derivatives bearing aryloxy and arylthio substituents are reported, and their synthesis and characterization through NMR, combustion analysis, and MALDI-MS are described. We also demonstrate the modification of indium tin oxide (ITO) substrates using the PA functionalized asymmetric Pc derivatives and monitoring their electrochemistry. The PA functionalized asymmetric Pcs were anchored to the ITO surface through chemisorption and their electrochemical properties characterized using cyclic voltammetry to investigate the effects of PA structure on the thermodynamics and kinetics of charge transfer. Ionization energies of the modified ITO surfaces were measured using ultraviolet photoemission spectroscopy.
合成了带有金属和游离碱 A(3)B 型不对称酞菁（Pc）的化合物，在不对称象限中，带有一个灵活的烷基连接体，其链长不同，末端带有一个膦酸（PA）基团。本文报道了两个带有芳氧基和芳硫基取代基的平行不对称 Pc 衍生物系列，并通过 NMR、燃烧分析和 MALDI-MS 对其进行了描述。我们还展示了通过 PA 功能化不对称 Pc 衍生物对氧化铟锡（ITO）衬底的修饰，并监测了它们的电化学性能。PA 功能化不对称 Pc 通过化学吸附固定在 ITO 表面上，并通过循环伏安法对其电化学性质进行了表征，以研究 PA 结构对电子转移热力学和动力学的影响。使用紫外光电子能谱法测量了修饰后的 ITO 表面的电离能。
