Repozytorium

π‐Extended Hexapyrrolylbenzenes: Exploring Charge‐Transfer Phenomena in Donor‐Acceptor Propellers

Autorzy

Daniel Matuszczyk

Yu Jin Lee

Seongsoo Kang

Piotr J. Chmielewski

Joanna Cybińska

Dongho Kim

Marcin Stępień

Rok wydania

2023

Czasopismo

Chemistry-A European Journal

Numer woluminu

29

Strony

e202302429/1-e202302429/9

DOI

10.1002/chem.202302429

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

A family of propeller-shaped donor-acceptor hexapyrrolylbenzenes (HPBs) were designed and synthesized by sequential nucleophilic substitution of hexafluorobenzene with π-extended pyrroles. In particular, four hybrids were obtained, containing various combinations of electron-rich and electron-poor acenaphthylene-fused pyrroles. Additionally, to probe the efficiency of ortho transfer interactions, a system was designed containing unique donor and acceptor subunits spatially separated with four unfunctionalized pyrroles. DFT calculations showed propeller-shaped geometries of all HPB molecules and separation of frontier molecular orbitals between donor and acceptor subunits. Steady-state and time-resolved photophysical measurements revealed charge-transfer (CT) character of the emission with strong positive dependence on solvent polarity. The principal CT pathway involves ortho-positioned pairs of donors and acceptors and requires bending of the acceptor in the excited state.

Słowa kluczowe

chromophores, charge transfer, computational chemistry, nucleophilic aromatic substitution, pyrroles

Adres publiczny

http://dx.doi.org/10.1002/chem.202302429

Strona internetowa wydawcy

onlinelibrary.wiley.com

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