Binuclear Copper(I) Complexes for Near‐Infrared Light‐Emitting Electrochemical Cells

Two binuclear heteroleptic Cu I complexes, namely Cu−NIR1 and Cu−NIR2, bearing rigid chelating diphosphines and π‐conjugated 2,5‐di(pyridin‐2‐yl)thiazolo[5,4‐ d ]thiazole as the bis ‐bidentate ligand are presented. The proposed dinuclearization strategy yields a large bathochromic shift of the emiss...

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Published inAngewandte Chemie International Edition Vol. 62; no. 38; p. e202305569
Main Authors Jouaiti, Abdelaziz, Ballerini, Lavinia, Shen, Hsiang‐Ling, Viel, Ronan, Polo, Federico, Kyritsakas, Nathalie, Haacke, Stefan, Huang, Yu‐Ting, Lu, Chin‐Wei, Gourlaouen, Christophe, Su, Hai‐Ching, Mauro, Matteo
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 18.09.2023
Wiley-VCH Verlag
EditionInternational ed. in English
Subjects
Antifungal agents
Charge transfer
Chelation
Chemical Sciences
Copper
Electrochemical cells
Electrochemistry
Electroluminescence
Emission
Emissions
Emitters
Excitation
Fabrication
Ligands
Luminescence
Near infrared radiation
Quantum efficiency
Phosphorescence
Light-Emitting Electrochemical Cells
Near-Infrared Emitters
Binuclear Complexes
Copper Complexes
Online AccessGet full text
ISSN1433-7851
1521-3773
1521-3773
DOI10.1002/anie.202305569

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Abstract Two binuclear heteroleptic Cu I complexes, namely Cu−NIR1 and Cu−NIR2, bearing rigid chelating diphosphines and π‐conjugated 2,5‐di(pyridin‐2‐yl)thiazolo[5,4‐ d ]thiazole as the bis ‐bidentate ligand are presented. The proposed dinuclearization strategy yields a large bathochromic shift of the emission when compared to the mononuclear counterparts (M1–M2) and enables shifting luminescence into the near‐infrared (NIR) region in both solution and solid state, showing emission maximum at ca. 750 and 712 nm, respectively. The radiative process is assigned to an excited state with triplet metal‐to‐ligand charge transfer ( 3 MLCT) character as demonstrated by in‐depth photophysical and computational investigation. Noteworthy, X‐ray analysis of the binuclear complexes unravels two interligand π–π‐stacking interactions yielding a doubly locked structure that disfavours flattening of the tetrahedral coordination around the Cu I centre in the excited state and maintain enhanced NIR luminescence. No such interaction is present in M1–M2. These findings prompt the successful use of Cu−NIR1 and Cu−NIR2 in NIR light‐emitting electrochemical cells (LECs), which display electroluminescence maximum up to 756 nm and peak external quantum efficiency (EQE) of 0.43 %. Their suitability for the fabrication of white‐emitting LECs is also demonstrated. To the best of our knowledge, these are the first examples of NIR electroluminescent devices based on earth‐abundant Cu I emitters.
AbstractList Two binuclear heteroleptic CuI complexes, namely Cu-NIR1 and Cu-NIR2, bearing rigid chelating diphosphines and π-conjugated 2,5-di(pyridin-2-yl)thiazolo[5,4-d]thiazole as the bis-bidentate ligand are presented. The proposed dinuclearization strategy yields a large bathochromic shift of the emission when compared to the mononuclear counterparts (M1-M2) and enables shifting luminescence into the near-infrared (NIR) region in both solution and solid state, showing emission maximum at ca. 750 and 712 nm, respectively. The radiative process is assigned to an excited state with triplet metal-to-ligand charge transfer (3 MLCT) character as demonstrated by in-depth photophysical and computational investigation. Noteworthy, X-ray analysis of the binuclear complexes unravels two interligand π-π-stacking interactions yielding a doubly locked structure that disfavours flattening of the tetrahedral coordination around the CuI centre in the excited state and maintain enhanced NIR luminescence. No such interaction is present in M1-M2. These findings prompt the successful use of Cu-NIR1 and Cu-NIR2 in NIR light-emitting electrochemical cells (LECs), which display electroluminescence maximum up to 756 nm and peak external quantum efficiency (EQE) of 0.43 %. Their suitability for the fabrication of white-emitting LECs is also demonstrated. To the best of our knowledge, these are the first examples of NIR electroluminescent devices based on earth-abundant CuI emitters.Two binuclear heteroleptic CuI complexes, namely Cu-NIR1 and Cu-NIR2, bearing rigid chelating diphosphines and π-conjugated 2,5-di(pyridin-2-yl)thiazolo[5,4-d]thiazole as the bis-bidentate ligand are presented. The proposed dinuclearization strategy yields a large bathochromic shift of the emission when compared to the mononuclear counterparts (M1-M2) and enables shifting luminescence into the near-infrared (NIR) region in both solution and solid state, showing emission maximum at ca. 750 and 712 nm, respectively. The radiative process is assigned to an excited state with triplet metal-to-ligand charge transfer (3 MLCT) character as demonstrated by in-depth photophysical and computational investigation. Noteworthy, X-ray analysis of the binuclear complexes unravels two interligand π-π-stacking interactions yielding a doubly locked structure that disfavours flattening of the tetrahedral coordination around the CuI centre in the excited state and maintain enhanced NIR luminescence. No such interaction is present in M1-M2. These findings prompt the successful use of Cu-NIR1 and Cu-NIR2 in NIR light-emitting electrochemical cells (LECs), which display electroluminescence maximum up to 756 nm and peak external quantum efficiency (EQE) of 0.43 %. Their suitability for the fabrication of white-emitting LECs is also demonstrated. To the best of our knowledge, these are the first examples of NIR electroluminescent devices based on earth-abundant CuI emitters.
Two binuclear heteroleptic Cu complexes, namely Cu-NIR1 and Cu-NIR2, bearing rigid chelating diphosphines and π-conjugated 2,5-di(pyridin-2-yl)thiazolo[5,4-d]thiazole as the bis-bidentate ligand are presented. The proposed dinuclearization strategy yields a large bathochromic shift of the emission when compared to the mononuclear counterparts (M1-M2) and enables shifting luminescence into the near-infrared (NIR) region in both solution and solid state, showing emission maximum at ca. 750 and 712 nm, respectively. The radiative process is assigned to an excited state with triplet metal-to-ligand charge transfer ( MLCT) character as demonstrated by in-depth photophysical and computational investigation. Noteworthy, X-ray analysis of the binuclear complexes unravels two interligand π-π-stacking interactions yielding a doubly locked structure that disfavours flattening of the tetrahedral coordination around the Cu centre in the excited state and maintain enhanced NIR luminescence. No such interaction is present in M1-M2. These findings prompt the successful use of Cu-NIR1 and Cu-NIR2 in NIR light-emitting electrochemical cells (LECs), which display electroluminescence maximum up to 756 nm and peak external quantum efficiency (EQE) of 0.43 %. Their suitability for the fabrication of white-emitting LECs is also demonstrated. To the best of our knowledge, these are the first examples of NIR electroluminescent devices based on earth-abundant Cu emitters.
Two binuclear heteroleptic CuI complexes, namely Cu−NIR1 and Cu−NIR2, bearing rigid chelating diphosphines and π‐conjugated 2,5‐di(pyridin‐2‐yl)thiazolo[5,4‐d]thiazole as the bis‐bidentate ligand are presented. The proposed dinuclearization strategy yields a large bathochromic shift of the emission when compared to the mononuclear counterparts (M1–M2) and enables shifting luminescence into the near‐infrared (NIR) region in both solution and solid state, showing emission maximum at ca. 750 and 712 nm, respectively. The radiative process is assigned to an excited state with triplet metal‐to‐ligand charge transfer (3MLCT) character as demonstrated by in‐depth photophysical and computational investigation. Noteworthy, X‐ray analysis of the binuclear complexes unravels two interligand π–π‐stacking interactions yielding a doubly locked structure that disfavours flattening of the tetrahedral coordination around the CuI centre in the excited state and maintain enhanced NIR luminescence. No such interaction is present in M1–M2. These findings prompt the successful use of Cu−NIR1 and Cu−NIR2 in NIR light‐emitting electrochemical cells (LECs), which display electroluminescence maximum up to 756 nm and peak external quantum efficiency (EQE) of 0.43 %. Their suitability for the fabrication of white‐emitting LECs is also demonstrated. To the best of our knowledge, these are the first examples of NIR electroluminescent devices based on earth‐abundant CuI emitters.
Two binuclear heteroleptic Cu I complexes, namely Cu−NIR1 and Cu−NIR2, bearing rigid chelating diphosphines and π‐conjugated 2,5‐di(pyridin‐2‐yl)thiazolo[5,4‐ d ]thiazole as the bis ‐bidentate ligand are presented. The proposed dinuclearization strategy yields a large bathochromic shift of the emission when compared to the mononuclear counterparts (M1–M2) and enables shifting luminescence into the near‐infrared (NIR) region in both solution and solid state, showing emission maximum at ca. 750 and 712 nm, respectively. The radiative process is assigned to an excited state with triplet metal‐to‐ligand charge transfer ( 3 MLCT) character as demonstrated by in‐depth photophysical and computational investigation. Noteworthy, X‐ray analysis of the binuclear complexes unravels two interligand π–π‐stacking interactions yielding a doubly locked structure that disfavours flattening of the tetrahedral coordination around the Cu I centre in the excited state and maintain enhanced NIR luminescence. No such interaction is present in M1–M2. These findings prompt the successful use of Cu−NIR1 and Cu−NIR2 in NIR light‐emitting electrochemical cells (LECs), which display electroluminescence maximum up to 756 nm and peak external quantum efficiency (EQE) of 0.43 %. Their suitability for the fabrication of white‐emitting LECs is also demonstrated. To the best of our knowledge, these are the first examples of NIR electroluminescent devices based on earth‐abundant Cu I emitters.
Two binuclear heteroleptic Cu I complexes, namely Cu−NIR1 and Cu−NIR2, bearing rigid chelating diphosphines and π‐conjugated 2,5‐di(pyridin‐2‐yl)thiazolo[5,4‐ d ]thiazole as the bis ‐bidentate ligand are presented. The proposed dinuclearization strategy yields a large bathochromic shift of the emission when compared to the mononuclear counterparts (M1–M2) and enables shifting luminescence into the near‐infrared (NIR) region in both solution and solid state, showing emission maximum at ca. 750 and 712 nm, respectively. The radiative process is assigned to an excited state with triplet metal‐to‐ligand charge transfer ( 3 MLCT) character as demonstrated by in‐depth photophysical and computational investigation. Noteworthy, X‐ray analysis of the binuclear complexes unravels two interligand π–π‐stacking interactions yielding a doubly locked structure that disfavours flattening of the tetrahedral coordination around the Cu I centre in the excited state and maintain enhanced NIR luminescence. No such interaction is present in M1–M2. These findings prompt the successful use of Cu−NIR1 and Cu−NIR2 in NIR light‐emitting electrochemical cells (LECs), which display electroluminescence maximum up to 756 nm and peak external quantum efficiency (EQE) of 0.43 %. Their suitability for the fabrication of white‐emitting LECs is also demonstrated. To the best of our knowledge, these are the first examples of NIR electroluminescent devices based on earth‐abundant Cu I emitters.
Author Haacke, Stefan
Polo, Federico
Gourlaouen, Christophe
Ballerini, Lavinia
Lu, Chin‐Wei
Huang, Yu‐Ting
Viel, Ronan
Kyritsakas, Nathalie
Mauro, Matteo
Su, Hai‐Ching
Shen, Hsiang‐Ling
Jouaiti, Abdelaziz
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Issue 38
Keywords Phosphorescence
Light-Emitting Electrochemical Cells
Near-Infrared Emitters
Binuclear Complexes
Copper Complexes
Language English
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Snippet Two binuclear heteroleptic Cu I complexes, namely Cu−NIR1 and Cu−NIR2, bearing rigid chelating diphosphines and π‐conjugated 2,5‐di(pyridin‐2‐yl)thiazolo[5,4‐...
Two binuclear heteroleptic Cu complexes, namely Cu-NIR1 and Cu-NIR2, bearing rigid chelating diphosphines and π-conjugated...
Two binuclear heteroleptic CuI complexes, namely Cu−NIR1 and Cu−NIR2, bearing rigid chelating diphosphines and π‐conjugated...
Two binuclear heteroleptic CuI complexes, namely Cu-NIR1 and Cu-NIR2, bearing rigid chelating diphosphines and π-conjugated...
Two binuclear heteroleptic Cu I complexes, namely Cu−NIR1 and Cu−NIR2, bearing rigid chelating diphosphines and π‐conjugated 2,5‐di(pyridin‐2‐yl)thiazolo[5,4‐...
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SubjectTerms Antifungal agents
Charge transfer
Chelation
Chemical Sciences
Copper
Electrochemical cells
Electrochemistry
Electroluminescence
Emission
Emissions
Emitters
Excitation
Fabrication
Ligands
Luminescence
Near infrared radiation
Quantum efficiency
Title Binuclear Copper(I) Complexes for Near‐Infrared Light‐Emitting Electrochemical Cells
URI https://www.ncbi.nlm.nih.gov/pubmed/37345993
https://www.proquest.com/docview/2864469961
https://www.proquest.com/docview/2828759227
https://hal.science/hal-04237725
Volume 62
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