Applications of Fluorous Porphyrinoids: An Update^†

Abstract

Porphyrins and related macrocycles have been studied broadly for their applications in medicine and materials because of their tunable physicochemical, optoelectronic and magnetic properties. In this review article, we focused on the applications of fluorinated porphyrinoids and their supramolecular systems and summarized the reports published on these chromophores in the past 5-6 years. The commercially available fluorinated porphyrinoids: meso-perfluorophenylporphyrin (TPPF 20 ) perfluorophthalocyanine (PcF 16 ) and meso-perfluorophenylcorrole (CorF 15 ) have increased photo and oxidative stability due to the presence of fluoro groups. Because of their tunable properties and robustness toward oxidative damage these porphyrinoidbased chromophores continue to gain attention of researchers developing advanced functional materials for applications such as sensors, photonic devices, component for solar cells, biomedical imaging, theranostics and catalysts.

Synthesis of new representatives of A3B-type carboranylporphyrins based on meso-tetra(pentafluorophenyl)porphyrin transformations

“…Nucleophilic substitution reactions of the four p-fluorine atoms in 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (1) are well studied [15][16][17][18][19][20][21][22][23][24][25][26][27]. In order to prepare boronated PSs of A 3 B-type the employed synthetic strategy included the preparation of monoazido-substituted tris(pentafluorophenyl)porphyrin 2 by the reaction of porphyrin 1 with sodium azide (molar ratio 1:1.9) in DMF at ambient temperature for 4 h. Under these reaction conditions, monoazide derivative 2 was obtained in 40% yield along with a mixture of porphyrin 1, di-and triazido-substituted derivatives.…”

“…We also studied the nucleophilic substitution reactions of the p-fluorine atom in the pentafluorophenyl-containing porphyrin 6 with thiol-substituted compounds such as 2-mercaptoethanol (15), cysteamine hydrochloride (16), and 3-chloro-1-propanethiol (17) as shown in Scheme 5.…”

“…The introduction of a fluorine atom into the molecule is the feasibility to change drastically its biological properties and to modify the profile of biological activity due to optimum fluorine lipophylic properties, and enhanced interaction with lipid membranes [12][13][14]. Pentafluorophenyl-substituted porphyrin systems are especially useful for the connection of various functionalities capable for coupling with biomolecules via the nucleophilic aromatic (S N Ar) substitution reactions [15,16]. A variety of nucleophiles such as amines [17,18], alcohols [18][19][20], thiols [17,19,[21][22][23], and carboranes [17,[24][25][26][27] have been studied in selective S N Ar substitution reactions of the p-fluorine atoms in meso-pentafluorophenyl-substituted porphyrins.…”

Porphyrin-based covalent organic frameworks from design, synthesis to biological applications

“…[6][7][8] Numerous porphyrins and their derivatives have been deliberately synthesized to serve diverse purposes, acting as catalysts, electron transport materials, DNA-binding or cleavage agents, photoluminescent molecules, and photosensitizers. 9,10 The conjugated macrocyclic structure of porphyrins furnishes a firm and stable coordination environment for central metals, rendering them compelling contenders for catalytic reactions involving various classes of metal-active centers. 11,12 Despite these merits, challenges arise due to potent π-π interactions between planar polyaromatic macrocycles, resulting in low solubility in aqueous solutions, susceptibility to agglomeration and deactivation, and a propensity to burst when employed as photosensitizers.…”