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Synthesis of Porphyrinoids, BODIPYs, and (Dipyrrinato)ruthenium(II) Complexes from Prefunctionalized Dipyrromethanes
Author(s) -
Hohlfeld Benjamin F.,
Flanagan Keith J.,
Kulak Nora,
Senge Mathias O.,
Christmann Mathias,
Wiehe Arno
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201900530
Subject(s) - chemistry , ruthenium , moiety , nucleophile , bodipy , nucleophilic aromatic substitution , amine gas treating , combinatorial chemistry , nucleophilic substitution , organic chemistry , fluorescence , catalysis , physics , quantum mechanics
The introduction of functional groups into the meso ‐position of dipyrromethanes, boron‐dipyrromethenes (BODIPYs) and porphyrinoids, is of fundamental importance in designing such dye systems for material sciences or photomedicine. One route that has proven to be particularly useful in this respect is the nucleophilic aromatic substitution (S N Ar) on porphyrinoids and their precursors carrying electron‐withdrawing substituents. To further expand this methodology, the potential of the 4‐fluoro‐3‐nitrophenyl and the 3,4,5‐trifluorophenyl moieties for the synthesis of functionalized dipyrromethanes, BODIPYs, and porphyrinoids has been evaluated. The 3,4,5‐trifluorophenyl moiety proved not to be applicable in the S N Ar with nucleophiles. The introduction of the 4‐fluoro‐3‐nitrophenyl group, however, allowed fast and efficient S N Ar with various amine nucleophiles. The synthesized 4‐amino‐3‐nitrophenyl‐substituted dipyrromethanes were successfully applied in the synthesis BODIPYs and were tested in the synthesis of “ trans ”‐A 2 B 2 porphyrins and A 2 B corroles. Furthermore, the dipyrromethanes – after oxidation to the dipyrromethenes – were found to be suitable ligands for metal ions giving access to functionalized ruthenium(II) metal complexes.