Department of Chemistry and Biochemistry, Hunter College and Graduate Center of the City University of New York (CUNY), 695 Park Avenue, New York, NY 10065, USA.
Org Biomol Chem. 2016 Jan 14;14(2):389-408. doi: 10.1039/c5ob01839k.
Porphyrinoids are robust heterocyclic dyes studied extensively for their applications in medicine and as photonic materials because of their tunable photophysical properties, diverse means of modifying the periphery, and the ability to chelate most transition metals. Commercial applications include their use as phthalocyanine dyes in optical discs, porphyrins in photodynamic therapy, and as oxygen sensors. Most applications of these dyes require exocyclic moieties to improve solubility, target diseases, modulate photophysical properties, or direct the self-organization into architectures with desired photonic properties. The synthesis of the porphyrinoid depends on the desired application, but the de novo synthesis often involves several steps, is time consuming, and results in low isolated yields. Thus, the application of core porphyrinoid platforms that can be rapidly and efficiently modified to evaluate new molecular architectures allows researchers to focus on the design concepts rather than the synthesis methods, and opens porphyrinoid chemistry to a broader scientific community. We have focused on several widely available, commercially viable porphyrinoids as platforms: meso-perfluorophenylporphyrin, perfluorophthalocyanine, and meso-perfluorophenylcorrole. The perfluorophenylporphyrin is readily converted to the chlorin, bacteriochlorin, and isobacteriochlorin. Derivatives of all six of these core platforms can be efficiently and controllably made via mild nucleophilic aromatic substitution reactions using primary S, N, and O nucleophiles bearing a wide variety of functional groups. The remaining fluoro groups enhance the photo and oxidative stability of the dyes and can serve as spectroscopic signatures to characterize the compounds or in imaging applications using (19)F NMR. This review provides an overview of the chemistry of fluorinated porphyrinoids that are being used as a platform to create libraries of photo-active compounds for applications in medicine and materials.
卟啉类化合物是一类稳定的杂环染料，由于其可调谐的光物理性质、多种多样的外围修饰方法以及与大多数过渡金属螯合的能力，在医学和光子材料领域得到了广泛的研究。商业应用包括将其用作光盘中的酞菁染料、光动力治疗中的卟啉以及氧传感器。这些染料的大多数应用都需要外生基团来提高溶解度、靶向疾病、调节光物理性质或指导自组装成具有所需光子特性的结构。卟啉类化合物的合成取决于所需的应用，但从头合成通常涉及多个步骤，耗时且产率低。因此，应用可以快速有效地进行修饰以评估新分子结构的核心卟啉类化合物平台，可以使研究人员专注于设计概念而不是合成方法，并将卟啉类化学扩展到更广泛的科学界。我们专注于几种广泛可用的、商业上可行的卟啉类化合物作为平台：间全氟苯基卟啉、全氟酞菁和间全氟苯基corrole。全氟苯基卟啉很容易转化为氯代卟啉、细菌叶绿素和异细菌叶绿素。所有这六种核心平台的衍生物都可以通过使用带有各种官能团的初级 S、N 和 O 亲核试剂的温和亲核芳香取代反应来高效且可控地制备。其余的氟基团增强了染料的光和氧化稳定性，并可作为光谱特征来表征化合物或在使用（19）F NMR 的成像应用中使用。本文综述了氟代卟啉类化合物的化学性质，这些化合物被用作创建光活性化合物库的平台，用于医学和材料领域的应用。
