Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 25, Issue 14, Pages 3525-3531Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201900022
Keywords
antiaromatic; expanded porphyrins; naphthorosarin; peripheral substitution; redox potential; stable radical cation (25pi)
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Funding
- Basic Science Research Program - National Research Foundation (NRF) under the Ministry of Science, ICT & Future Planning of Korea [2018R1A2A1A05077540]
- Samsung Research Funding & Incubation Center of Samsung Electronics [SRFC-MA1702-05]
- GRRC program of Gyeonggi province [GRRC-KyungHee2017(B01)]
- University-Industry Cooperation Foundation at KNU [520170528]
- National Institutes of Health [RGM103790A]
- Robert A. Welch Foundation [F-0018]
- National Research Foundation of Korea [2018R1A2A1A05077540] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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Peripherally substituted antiaromatic naphthorosarins have been synthesized for the first time. The synthesis was accomplished by acid-catalyzed condensation of naphthobipyrrole building blocks with aromatic aldehydes. The naphthobipyrrole building blocks were synthesized by simple oxidative coupling of the corresponding pyrrole substituted aromatics. Solid-state structural analyses of the synthesized naphthorosarins revealed that the presence of meso-2,6-dichlorophenyl- and 5,6-difluoro-substitution substantially alter the geometry and properties of the naphthorosarins. The substituents affect the redox potentials as well and, in turn, the proton-coupled electron-transfer processes leading to the formation of one- and two-electron reduced forms of the corresponding naphthorosarins. One particular naphthorosarin that bears both peripheral fluorine and meso-2,6-dichlorophenyl substituents forms a stable 25 pi-electron species upon treating with TFA that was characterized by single-crystal X-ray diffraction analysis. The current study underscores how structural modifications can be used to fine-tune the electronic features of naphthorosarins, including stabilization of odd electron species.
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