Fe( iii )-Catalyzed synthesis of pyrrolo[3,2- b ]pyrroles: formation of new dyes and photophysical studies - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Organic Chemistry Frontiers Année : 2019

Fe( iii )-Catalyzed synthesis of pyrrolo[3,2- b ]pyrroles: formation of new dyes and photophysical studies

Mariusz Tasior
Beata Koszarna
David Young
Beata Bernard
  • Fonction : Auteur
Dorota Gryko
Daniel Gryko

Résumé

The multicomponent reaction of primary aromatic amines, aromatic aldehydes and biacetyl leads to 1,2,4,5-tetraarylpyrrolo[3,2-b]pyrroles in yields as large as 77% when catalyzed by iron(III) perchlorate. These new conditions enabled for the first time, the synthesis of pyrrolo[3,2-b]pyrroles from 5-membered heterocyclic aldehydes such as furan, thiophene, thiazole, and their benzo derivatives as well as from 1-aminonaphthalene, 3,5-bis(trifluoromethyl)aniline, and hexane-3,4-dione. Photophysical studies have revealed that pyrrolo[3,2-b]pyrroles possessing five-membered rings at positions 2 and 5 have large fluorescence quantum yields as well as bathochromicaly shifted absorption and emission compared to tetraphenyl-pyrrolopyrroles; the shift being particularly marked for both furan and benzofuran. Large Stokes shifts can be attained when substituents bearing multiple biaryl linkages are present at positions 2 and 5. The new fluorphores’ optical properties were rationalized through ab initio calculations relying on Time-Dependent Density Functional Theory (TD-DFT) and second-order Coupled Cluster (CC2) methods. These computational studies confirmed that low dihedral angles are the main cause for bathochromically shifted absorption and emission for pyrrolo[3,2-b]pyrroles bearing five-membered aromatic heterocycles.

Domaines

Chimie
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Dates et versions

hal-03454178 , version 1 (29-11-2021)

Identifiants

Citer

Mariusz Tasior, Beata Koszarna, David Young, Beata Bernard, Denis Jacquemin, et al.. Fe( iii )-Catalyzed synthesis of pyrrolo[3,2- b ]pyrroles: formation of new dyes and photophysical studies. Organic Chemistry Frontiers, 2019, 6 (16), pp.2939-2948. ⟨10.1039/C9QO00675C⟩. ⟨hal-03454178⟩
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