Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores

Jiawang Zhou; Ljiljana Stojanović; Andrey A. Berezin; Tommaso Battisti; Abigail Gill; Benson M. Kariuki; Davide Bonifazi; Rachel Crespo-Otero; Michael R. Wasielewski; Yi Lin Wu

doi:10.1039/d0sc04646a

Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores

Jiawang Zhou, Ljiljana Stojanović, Andrey A. Berezin, Tommaso Battisti, Abigail Gill, Benson M. Kariuki, Davide Bonifazi, Rachel Crespo-Otero, Michael R. Wasielewski, Yi Lin Wu

Chemistry

Research output: Contribution to journal › Article › peer-review

35 Scopus citations

Abstract

Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.

Original language	English (US)
Pages (from-to)	767-773
Number of pages	7
Journal	Chemical Science
Volume	12
Issue number	2
DOIs	https://doi.org/10.1039/d0sc04646a
State	Published - Jan 14 2021

Funding

D. B. gratefully acknowledges the EU through the MSCA-ITN-ETN (GA No. 722591 – project PHOTOTRAIN) and School of Chemistry at Cardiff University for generous nancial support. R. C.-O. acknowledges funding from the EPSRC (EP/R029385/1) and Leverhulme Trust (RPG-2019-122). This research utilised Queen Mary's Apocrita HPC facility. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0020168 (M. R. W.). The authors thank Professor Kenneth D. M. Harris and Dr Colan E. Hughes (Cardiff) for the help with powder X-ray diffraction. D. B. gratefully acknowledges the EU through the MSCA-ITN-ETN (GA No. 722591 - project PHOTOTRAIN) and School of Chemistry at Cardiff University for generous financial support. R. C.-O. acknowledges funding from the EPSRC (EP/R029385/1) and Leverhulme Trust (RPG-2019-122). This research utilised Queen Mary's Apocrita HPC facility. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0020168 (M. R. W.). The authors thank Professor Kenneth D. M. Harris and Dr Colan E. Hughes (Cardiff) for the help with powder X-ray diffraction.

ASJC Scopus subject areas

General Chemistry

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10.1039/d0sc04646a

Cite this

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title = "Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores",

abstract = "Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.",

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AU - Battisti, Tommaso

AU - Gill, Abigail

AU - Kariuki, Benson M.

AU - Bonifazi, Davide

AU - Crespo-Otero, Rachel

AU - Wasielewski, Michael R.

AU - Wu, Yi Lin

PY - 2021/1/14

Y1 - 2021/1/14

N2 - Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.

AB - Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.

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Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores

Abstract

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CCDC 1949883: Experimental Crystal Structure Determination

CCDC 1949875: Experimental Crystal Structure Determination

CCDC 1949880: Experimental Crystal Structure Determination

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Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores

Abstract

Funding

ASJC Scopus subject areas

Access to Document

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Datasets

CCDC 1949883: Experimental Crystal Structure Determination

CCDC 1949875: Experimental Crystal Structure Determination

CCDC 1949880: Experimental Crystal Structure Determination

Cite this