Pistner Allen J, Yap Glenn P A, Rosenthal Joel
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716.
J Phys Chem C Nanomater Interfaces. 2012 Aug 16;116(32):16918-168924. doi: 10.1021/jp3059382. Epub 2012 Aug 2.
Porphyrins are attractive chromophores for incorporation into light harvesting devices. Some of the most efficient porphyrin derivatives in this regard are synthetically complex platforms with specially tailored electronic properties. This work details the unique geometric and electronic structure of the phlorin framework. X-ray crystallography and NMR spectroscopy demonstrate that unlike typical tetrapyrrole macrocycles, the phlorin is not aromatic. These unusual electronics are manifest in distinct photophysical and redox properties, as the phlorin displays a rich multielectron redox chemistry. The phlorin also displays an intriguing supramolecular chemistry and can reversibly bind up to two equivalents of fluoride in cooperative fashion. Accordingly, this synthetically accessible sensitizer displays a rich multielectron redox chemistry, excellent spectral coverage and an intriguing anion binding chemistry that distinguishes this system from more commonly studied porphyrinoids.
卟啉是用于整合到光收集装置中的有吸引力的发色团。在这方面，一些最有效的卟啉衍生物是具有特殊定制电子性质的合成复杂平台。这项工作详细阐述了卟吩骨架独特的几何和电子结构。X射线晶体学和核磁共振光谱表明，与典型的四吡咯大环不同，卟吩不是芳香性的。这些不寻常的电子特性表现为独特的光物理和氧化还原性质，因为卟吩显示出丰富的多电子氧化还原化学性质。卟吩还表现出有趣的超分子化学性质，并且可以以协同方式可逆地结合多达两个当量的氟化物。因此，这种可通过合成获得的敏化剂显示出丰富的多电子氧化还原化学性质、出色的光谱覆盖范围以及有趣的阴离子结合化学性质，这使得该体系有别于更常研究的卟啉类化合物。
