Comparative Synthetic Strategies for the Generation of 5,10‐ and 5,15‐Substituted Push‐Pull Porphyrins

• Published in: European journal of organic chemistry Vol. 2017; no. 25; pp. 3565 - 3583
• Main Authors: Meindl, Alina, Plunkett, Shane, Ryan, Aoife A., Flanagan, Keith J., Callaghan, Susan, Senge, Mathias O.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 07-07-2017
• Subjects: Demand analysis; Dye-sensitized solar cells; Electronic properties; Libraries; Nonlinear optics; Photovoltaic cells; Porphyrinoids; Porphyrins; Push‐pull systems; Sensitizers; Substituent effects; Synthesis; Synthetic methods
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201700093

Contemporary applications in optics, medicine, solar cells, or material science are increasingly reliant on unsymmetrically substituted porphyrins. Due to their widespread applications and rise in demand we undertook a comparative analysis of synthetic strategies for meso‐substituted porphyrins and present the synthesis of five different series of so‐called A2BC push‐pull porphyrins. The synthetic pathways used were applied to both 5,15‐substituted and 5,10‐substituted porphyrins, showcasing their flexibility and adaptability for different needs. Our approach combines well‐known reactions with a strategic and logical stepwise functionalization allowing researchers to change and modify the electronic properties of these systems at various points of the syntheses. This facilitates the easy optimization of the synthesis of systems of current interest, for example, porphyrins for dye‐sensitized solar cells (DSSCs) or for use in nonlinear optics, as well as fast generation of compound libraries.
In view of the applications of A2BC push‐pull porphyrins, for example in dye‐sensitized solar cells (DSSCs), we analyzed the synthetic strategies for 5,10‐ and 5,15‐substituted porphyrins, combining well‐known reactions with a strategic and logical stepwise functionalization, enabling the modification of the electronic properties of these systems at various points of the syntheses.