Développement de nouveaux complexes cationiques du cuivre pour l'élaboration de cellules électroluminescentes blanches

De nouveaux complexes de cuivre(I) cationiques de formule générale [Cu(P^P)(N^N)][PF6] où P^P représente un ligand bis-phosphine chélatant, bis-[2- (diphenylphosphino)phenyl]ether (DPEPhos) et N^N, des ligands 2,2-bis-pyridyls ont été développés. Les complexes ont montré des émissions à l’état solide couvrant tout le spectre du visible et la présence de la fluorescence retardée activée thermiquement (TADF) a été démontrée. Ces complexes ont été évaluées dans des cellules électrochimiques luminescentes (LECs) et ont conduit aux LECs émettant dans de différentes couleurs, i.e., bleue, verte, jaune, orange, rouge, et enfin des LECs blanches.New cationic copper(I) complexes with the general formula of [Cu(P^P)(N^N)][PF6] where P^P is a chelating bis-phosphine ligand bis-[2-(diphenylphosphino)phenyl]ether (DPEPhos) and N^N 2,2-bis-pyridyl ligand derivatives were developed. The complexes featured solid-state emissions covering the entire visible spectrum and the presence of the thermally activated delayed fluorescence (TADF) was demonstrated. Furthermore, the complexes were incorporated in light-emitting electrochemical cells (LEC) and led to devices emitting in different colors, i.e., blue, green, yellow, orange, red, and ultimately white-emitting LECs

Desarrollo de nuevos complejos catiónicos de cobre(I) para celdas electroquímicas emisoras de luz blanca

Tesis Doctoral inédita cotutelada por la Universidad de Caen Normandia y la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Física de Materiales. Fecha de Lectura: 16-12-2021Esta tesis tiene embargado el acceso al texto completo hasta el 16-06-2023The overall aim of this project was to design new cationic copper(I) complexes with emissions covering the entire visible spectrum and their incorporation into lightemitting electrochemical cells (LEC) towards the development of devices emitting in different colors, i.e., blue, green, yellow, orange, red and ultimately white-emitting LECs. The first focus was to develop complexes with the general formula of [Cu(P^P)(N^N)][PF6] where P^P is a chelating bis-phosphine ligand and N^N are 2,2- bispyridyl ligand derivatives. The commercially available bis-[2- (diphenylphosphino)phenyl]ether (DPEPhos) was chosen as the standard P^P chelating ligand, while the role of the N^N ligand was investigated by studying the influence of the central atom, the nature of the heteroaromatic ring, and electron-withdrawing groups like CF3. These complexes featured blue to red emissions with thermally activated delayed fluorescence (TADF). The structural, photophysical, electrochemical, and thermal properties of the complexes were investigated, and the most promising complexes were evaluated in LECs. Furthermore, white-emitting LECs were achieved using a host-guest approach. The results of this project are described herein. To make the reader familiar with the topic, this manuscript starts with the introduction of the solidstate lighting technology followed by the state of the art of copper(I) complexes in LECs in the first chapter. Then, the second chapter describes the synthesis and characterization of the copper(I) complexes in solution and powder, while the third chapter focuses on the thin-film characterization of the complexes and the design and characterization of LEC devices. Finally, the conclusions and future outlooks are discussed in the last part of the thesi

Cytotoxicity of cationic NHC copper(I) complexes coordinated to 2,2'-bis-pyridyl ligands

International audienceCytotoxicity of cationic (NHC)Cu(I) complexes bearing 2,2′-dipyridylamine (dpa) type ligands has been evaluated toward 4 cancer cell lines, and compared to the one of neutral (NHC)Cu(I) complexes. The high cytotoxicity of these novel cationic (NHC)Cu(I) complexes, combined with the straightforward synthesis, and versatility of dpa type ligands may offer new prospects in cancer research, toward the development of novel carrier linked prodrugs

Recent Advances in Solid-State Lighting Devices Using Transition Metal Complexes Exhibiting Thermally Activated Delayed Fluorescent Emission Mechanism

International audienceThis review focuses on the state-of-the-art of solid-state lighting devices (SSLDs)—that is, organic light-emitting diodes (OLEDs) and light-emitting electrochemical cells (LECs)—prepared with transition metal complexes featuring thermally activated delayed fluorescence (TADF) mechanism. First, the TADF mechanism is briefly introduced, as well as the experimental and theoretical methods applied to study TADF in transition metal complexes. Second, the review presents an exhaustive overview of OLED and LEC devices incorporating organometallic TADF emitters. For each type of device, the description of TADF is organized by respective elements focusing on each emission color, that is, blue, green/yellow, orange/red and, if existing, white. Finally, insights and future potential development of organometallic TADF emitters for lighting devices are comprehensively discussed. Overall, this review complements recent ones focused on TADF small molecules applied to the SSLD field

Recent advances in solid‐state lighting devices using transition metal complexes exhibiting thermally activated delayed fluorescent emission mechanism

This review focuses on the state‐of‐the‐art of solid‐state lighting devices (SSLDs)—that is, organic light‐emitting diodes (OLEDs) and light‐emitting electrochemical cells (LECs)—prepared with transition metal complexes featuring thermally activated delayed fluorescence (TADF) mechanism. First, the TADF mechanism is briefly introduced, as well as the experimental and theoretical methods applied to study TADF in transition metal complexes. Second, the review presents an exhaustive overview of OLED and LEC devices incorporating organometallic TADF emitters. For each type of device, the description of TADF is organized by respective elements focusing on each emission color, that is, blue, green/yellow, orange/red and, if existing, white. Finally, insights and future potential development of organometallic TADF emitters for lighting devices are comprehensively discussed. Overall, this review complements recent ones focused on TADF small molecules applied to the SSLD field.This work was supported by the “Ministère de la Recherche et des Nouvelles Technologies,” CNRS (Centre National de la Recherche Scientifique), and the LABEX SynOrg (ANR‐11‐LABX‐0029). The authors thank Normandie University (G.U.M.) for funding. R.D.C. acknowledges the program “Ayudas para la atracción de talento investigador – Modalidad 1 of the Consejería de Educación, Juventud y Deporte—Comunidad de Madrid with the reference number 2016‐T1/IND‐1463.” R.D.C. acknowledges Spanish MINECO for the Ramón y Cajal program (RYC‐2016‐20891), the Europa Excelencia program (ERC2019‐092825), the 2018 Leonardo Grant for Researchers and Cultural Creators from BBVA Foundation, and FOTOART‐CM project funded by Madrid region under programme P2018/NMT‐4367. J.F.‐C. acknowledges the Marie Skłodowska‐Curie Individual Fellowships (H2020‐MSCA‐IF‐2017).Peer reviewe

Recent Advances in Solid‐State Lighting Devices Using Transition Metal Complexes Exhibiting Thermally Activated Delayed Fluorescent Emission Mechanism

This review focuses on the state‐of‐the‐art of solid‐state lighting devices (SSLDs)—that is, organic light‐emitting diodes (OLEDs) and light‐emitting electrochemical cells (LECs)—prepared with transition metal complexes featuring thermally activated delayed fluorescence (TADF) mechanism. First, the TADF mechanism is briefly introduced, as well as the experimental and theoretical methods applied to study TADF in transition metal complexes. Second, the review presents an exhaustive overview of OLED and LEC devices incorporating organometallic TADF emitters. For each type of device, the description of TADF is organized by respective elements focusing on each emission color, that is, blue, green/yellow, orange/red and, if existing, white. Finally, insights and future potential development of organometallic TADF emitters for lighting devices are comprehensively discussed. Overall, this review complements recent ones focused on TADF small molecules applied to the SSLD field.This work was supported by the “Ministère de la Recherche et des Nouvelles Technologies,” CNRS (Centre National de la Recherche Scientifique), and the LABEX SynOrg (ANR‐11‐LABX‐0029). The authors thank Normandie University (G.U.M.) for funding. R.D.C. acknowledges the program “Ayudas para la atracción de talento investigador – Modalidad 1 of the Consejería de Educación, Juventud y Deporte—Comunidad de Madrid with the reference number 2016‐T1/IND‐1463.” R.D.C. acknowledges Spanish MINECO for the Ramón y Cajal program (RYC‐2016‐20891), the Europa Excelencia program (ERC2019‐092825), the 2018 Leonardo Grant for Researchers and Cultural Creators from BBVA Foundation, and FOTOART‐CM project funded by Madrid region under programme P2018/NMT‐4367. J.F.‐C. acknowledges the Marie Skłodowska‐Curie Individual Fellowships (H2020‐MSCA‐IF‐2017).Peer reviewe

Continuous flow ring-closing metathesis, an environmentally-friendly route to 2,5-dihydro-1H-pyrrole-3-carboxylates

International audienc

Design Rule Hidden from The Eye in S/N-Bridged Ancillary Ligands for Copper(I) Complexes Applied to Light-Emitting Electrochemical Cells

Enhancing low-energy emitting Cu(I)-ionic transition metal complexes (iTMCs) light-emitting electrochemical cells (LECs) is of utmost importance towards Cu(I)-iTMC-based white-emitting LECs. Here, the ancillary ligand design includes (i) extension of &amp; pi;-systems and (ii) insertion of S-bridge between heteroaromatics rings. This led to two novel heteroleptic Cu(I)-iTMCs: 2-(pyridin-2-yl-l2-azanyl)quinoline (CuN2) and 2-(naphthalen-2-ylthio)quinoline (CuS2) as N&amp;lt;^&amp;gt;N and bis[(2-diphenylphosphino)phenyl] ether as P&amp;lt;^&amp;gt;P, exhibiting improved photoluminescence quantum yields (&amp; phi;) and thermally activated delayed fluorescence processes compared to their reference Cu(I)-iTMCs: di(pyridin-2-yl)-l2-azane (CuN1) and di(pyridin-2-yl)sulfane (CuS1). Despite CuS2 stands out with the highest &amp; phi; (38% vs 17 / 14 / 1% for CuN1 / CuN2 / CuS1), only CuN2-LECs show the expected enhanced performance (0.35 cd A(-1) at luminance of 117 cd m(-2)) compared to CuN1-LECs (0.02 cd A(-1) at6 cd m(-2)), while CuS2-LECs feature low performances (0.04 cd A(-1) at 10 cd m(-2)). This suggests that conventional chemical design rules are not effective towards enhancing device performance. Herein, nonconventional multivariate statistical analysis and electrochemical impedance spectroscopy studies allow to rationalize the mismatch between chemical design and device performance bringing to light a hidden design rule: polarizability of the ancillary ligand is key for an efficient Cu(I)-iTMC-LECs. All-in-all, this study provides fresh insights for the design of Cu-iTMCs fueling research on sustainable ion-based lighting sources.Funding Agencies|European Union [956923]; CNRS (Centre National de la Recherche Scientifique); LABEX SynOrg [ANR-11-LABX-0029]; Normandie University; Projekt DEAL; Ministere de lEnseignement Superieur et de la Recherche; Region Normandie; Graduate School of Research XL-Chem [ANR-18-EURE-0020 XL-Chem]</p

New copper-based materials for White Light-emitting Electrochemical Cells (LEC) applications

International audienc

Towards rainbow photo/electro-luminescence in copper( i ) complexes with the versatile bridged bis-pyridyl ancillary ligand

International audienceThe synthesis and characterization of a family of copper( i ) complexes bearing a bridged bis-pyridyl ancillary ligand is reported, highlighting how the bridge nature impacts the photo- and electro-luminescent behaviours within the family