Perylene bisimide (PBI) dyes are known as red, maroon and black pigments, whose colors depend on the close π-π stacking arrangement. However, contrary to the luminescent monomers, deep-red and black PBI pigments are commonly non- or only weakly fluorescent due to (multiple) quenching pathways. Here, we introduce N-alkoxybenzyl substituted PBIs that contain close π stacking arrangement (exhibiting π-π ≈ 3.5 A, and longitudinal and transversal displacements of 3.1 A and 1.3 A; however, they afford deep-red emitters with solid-state fluorescence quantum yields (ΦF) of up to 60%. Systematic photophysical and computational studies in solution and in the solid state reveal a sensitive interconversion of the PBI-centred locally excited state and a charge transfer state, which depends on the dihedral angle ($þeta$) between the benzyl and alkoxy groups. This effectively controls the emission process, and enables high ΦF by circumventing the common quenching pathways commonly observed for perylene black analogues.
%0 Journal Article
%1 Tang2023
%A Tang, Ningning
%A Zhou, Jiadong
%A Wang, Liangxuan
%A Stolte, Matthias
%A Xie, Guojing
%A Wen, Xinbo
%A Liu, Linlin
%A Würthner, Frank
%A Gierschner, Johannes
%A Xie, Zengqi
%D 2023
%J Nat. Commun.
%K myown
%N 1
%P 1922
%R 10.1038/s41467-023-37171-y
%T Anomalous deep-red luminescence of perylene black analogues with strong π-π interactions
%U https://doi.org/10.1038/s41467-023-37171-y
%V 14
%X Perylene bisimide (PBI) dyes are known as red, maroon and black pigments, whose colors depend on the close π-π stacking arrangement. However, contrary to the luminescent monomers, deep-red and black PBI pigments are commonly non- or only weakly fluorescent due to (multiple) quenching pathways. Here, we introduce N-alkoxybenzyl substituted PBIs that contain close π stacking arrangement (exhibiting π-π ≈ 3.5 A, and longitudinal and transversal displacements of 3.1 A and 1.3 A; however, they afford deep-red emitters with solid-state fluorescence quantum yields (ΦF) of up to 60%. Systematic photophysical and computational studies in solution and in the solid state reveal a sensitive interconversion of the PBI-centred locally excited state and a charge transfer state, which depends on the dihedral angle ($þeta$) between the benzyl and alkoxy groups. This effectively controls the emission process, and enables high ΦF by circumventing the common quenching pathways commonly observed for perylene black analogues.
@article{Tang2023,
abstract = {Perylene bisimide (PBI) dyes are known as red, maroon and black pigments, whose colors depend on the close π-π stacking arrangement. However, contrary to the luminescent monomers, deep-red and black PBI pigments are commonly non- or only weakly fluorescent due to (multiple) quenching pathways. Here, we introduce N-alkoxybenzyl substituted PBIs that contain close π stacking arrangement (exhibiting π-π ≈ 3.5 A, and longitudinal and transversal displacements of 3.1 A and 1.3 A; however, they afford deep-red emitters with solid-state fluorescence quantum yields (ΦF) of up to 60%. Systematic photophysical and computational studies in solution and in the solid state reveal a sensitive interconversion of the PBI-centred locally excited state and a charge transfer state, which depends on the dihedral angle ($\theta$) between the benzyl and alkoxy groups. This effectively controls the emission process, and enables high ΦF by circumventing the common quenching pathways commonly observed for perylene black analogues.},
added-at = {2024-07-22T14:06:15.000+0200},
author = {Tang, Ningning and Zhou, Jiadong and Wang, Liangxuan and Stolte, Matthias and Xie, Guojing and Wen, Xinbo and Liu, Linlin and Würthner, Frank and Gierschner, Johannes and Xie, Zengqi},
biburl = {https://www.bibsonomy.org/bibtex/2136b1fc680fd1331f6168de4e0b109c4/wuerthner_group},
day = 06,
doi = {10.1038/s41467-023-37171-y},
interhash = {2146140aa74c3e538831b1b132f73336},
intrahash = {136b1fc680fd1331f6168de4e0b109c4},
issn = {2041-1723},
journal = {Nat. Commun.},
keywords = {myown},
month = apr,
number = 1,
pages = 1922,
timestamp = {2024-11-26T10:01:13.000+0100},
title = {Anomalous deep-red luminescence of perylene black analogues with strong π-π interactions},
url = {https://doi.org/10.1038/s41467-023-37171-y},
volume = 14,
year = 2023
}