0000000000087721
AUTHOR
Rosario Scopelliti
Near-UV to red-emitting charged bis-cyclometallated iridium(iii) complexes for light-emitting electrochemical cells
Herein we report a series of charged iridium complexes emitting from near-UV to red using carbene-based N^C: ancillary ligands. Synthesis, photophysical and electrochemical properties of this series are described in detail together with X-ray crystal structures. Density Functional Theory calculations show that the emission originates from the cyclometallated main ligand, in contrast to commonly designed charged complexes using bidentate N^N ancillary ligands, where the emission originates from the ancillary N^N ligand. The radiative process of this series of compounds is characterized by relatively low photoluminescence quantum yields in solution that is ascribed to non-radiative deactivati…
Acetylenes Rearranging on Ruthenium-Porphyrinogen and Leading to Vinylidene and Carbene Functionalities.
Through a proton-transfer reaction a porphyrinogen assists the transformation of terminal acetylenes into Ru-vinylidenes, which are the entry point to a variety of Ru-carbenes and Ru-cumulenes. The scheme (in which the porphyrinogen is stylized) shows the reversible interconversion of an acetylide into a divinylidene unit.
Efficient orange light-emitting electrochemical cells
We report the first bis-cyclometalated cationic iridium(III) complex with N-aryl-substituted 1H-imidazo [4,5-f][1,10]phenanthroline. The complex emits yellow-orange phosphorescence with a maximum at 583 nm, a quantum yield of 43%, and an excited-state lifetime of 910 ns in argon-saturated dichloromethane. Optimized orange light-emitting electrochemical cells with the new Ir(III) complex exhibit fast turn-on, a peak luminance of 684 cd m(-2) and a peak efficacy of 6.5 cd A(-1); in 850 h of continuous operation their luminance and efficacy decrease only by 20%.
A deep-blue emitting charged bis-cyclometallated iridium(iii) complex for light-emitting electrochemical cells
We report here a new cationic bis-cyclometallated iridium(III) complex, 1, with deep-blue emission at 440 nm and its use in Light-emitting Electrochemical Cells (LECs). The design is based on the 2′,6′-difluoro-2,3′-bipyridine skeleton as the cyclometallating ligand and a bis-imidazolium carbene-type ancillary ligand. Furthermore, bulky tert-butyl substituents are used to limit the intermolecular interactions. LECs have been driven both at constant voltage (6 V) and constant current (2.5 mA cm−2). The performances are significantly improved with the latter method, resulting overall in one of the best reported greenish-blue LECs having fast response (17 s), light intensity over 100 cd m−2 an…
Synthesis, crystal structure and magnetic properties of the chiral iron(II) chain [Fe(bpym)(NCS)2]n (bpym = 2,2′-bipyrimidine)
Abstract The iron(II) compound of formula [Fe(bpym)(NCS)2]n (bpym = 2,2′-bipyrimidine) has been synthesized and its crystal structure determined by X-ray diffraction methods. It crystallizes in the tetragonal P41 (No. 76) and P43 space groups, a = 8.849(2), c=16.486(3) A , V=1290.9(5) A 3 , Z=4, D c =1.699 g cm −3 , M r =330.2, F(000)=664, λ( Mo K α)=0.71073 A , μ( Mo K α)=14.8 cm −1 and T=295 K. A total of 2449 reflections was collected over the range 3≤2ϑ≤55°; of these, 1657 were unique and 1321 were considered as observed (13σ(I)) and used in the structural analysis. The final R and Rw residuals were 0.027 and 0.026, respectively. The structure is made up of chiral (Δ and Λ enantiomers c…
Pulsed-current versus constant-voltage light-emitting electrochemical cells with trifluoromethyl-substituted cationic iridium(iii) complexes
We report on five cationic iridium(III) complexes with cyclometalating 2-(3′-trifluoromethylphenyl)pyridine and a diimine, [(C⁁N)2Ir(N⁁N)](PF6), N⁁N = 4,4′-R2-2,2′-dipyridyl or 4,7-R2-1,10-phenanthroline (R = H, Me, tert-Bu, Ph), and characterize three of them by crystal structure analysis. The complexes undergo oxidation of the Ir–aryl fragment at 1.13–1.16 V (against ferrocene couple) and reduction of the N⁁N ligand at −1.66 V to −1.86 V, and have a redox gap of 2.84–2.99 V. The complexes exhibit bluish-green to green-yellow phosphorescence in an argon-saturated dichloromethane solution at room temperature with a maximum at 486–520 nm, quantum yield of 61–67%, and an excited-state lifetim…
An Ester-Substituted Iridium Complex for Efficient Vacuum-Processed Organic Light-Emitting Diodes
An orange-red-emitting iridium complex (N958) was prepared, and its photophysical and device-based characteristics were investigated. Despite N958 displaying quite poor photophysical properties in solution (acetonitrile), organic light-emitting diode (OLED) devices based on the complex exhibit an efficiency close to 10%.
CCDC 968510: Experimental Crystal Structure Determination
Related Article: Filippo Monti, Florian Kessler, Manuel Delgado, Julien Frey, Federico Bazzanini, Gianluca Accorsi, Nicola Armaroli, Henk J. Bolink, Enrique Ortí, Rosario Scopelliti, Md. Khaja Nazeeruddin, and Etienne Baranoff|2013|Inorg.Chem.|52|10292|doi:10.1021/ic400600d
CCDC 968508: Experimental Crystal Structure Determination
Related Article: Filippo Monti, Florian Kessler, Manuel Delgado, Julien Frey, Federico Bazzanini, Gianluca Accorsi, Nicola Armaroli, Henk J. Bolink, Enrique Ortí, Rosario Scopelliti, Md. Khaja Nazeeruddin, and Etienne Baranoff|2013|Inorg.Chem.|52|10292|doi:10.1021/ic400600d
CCDC 968506: Experimental Crystal Structure Determination
Related Article: Filippo Monti, Florian Kessler, Manuel Delgado, Julien Frey, Federico Bazzanini, Gianluca Accorsi, Nicola Armaroli, Henk J. Bolink, Enrique Ortí, Rosario Scopelliti, Md. Khaja Nazeeruddin, and Etienne Baranoff|2013|Inorg.Chem.|52|10292|doi:10.1021/ic400600d
CCDC 914725: Experimental Crystal Structure Determination
Related Article: Nail M. Shavaleev, Rosario Scopelliti, Michael Grätzel, Mohammad K. Nazeeruddin, Antonio Pertegás, Cristina Roldán-Carmona, Daniel Tordera and Henk J. Bolink|2013|J.Mater.Chem.C|1|2241|doi:10.1039/C3TC00808H
CCDC 914726: Experimental Crystal Structure Determination
Related Article: Nail M. Shavaleev, Rosario Scopelliti, Michael Grätzel, Mohammad K. Nazeeruddin, Antonio Pertegás, Cristina Roldán-Carmona, Daniel Tordera and Henk J. Bolink|2013|J.Mater.Chem.C|1|2241|doi:10.1039/C3TC00808H
CCDC 968507: Experimental Crystal Structure Determination
Related Article: Filippo Monti, Florian Kessler, Manuel Delgado, Julien Frey, Federico Bazzanini, Gianluca Accorsi, Nicola Armaroli, Henk J. Bolink, Enrique Ortí, Rosario Scopelliti, Md. Khaja Nazeeruddin, and Etienne Baranoff|2013|Inorg.Chem.|52|10292|doi:10.1021/ic400600d
CCDC 914724: Experimental Crystal Structure Determination
Related Article: Nail M. Shavaleev, Rosario Scopelliti, Michael Grätzel, Mohammad K. Nazeeruddin, Antonio Pertegás, Cristina Roldán-Carmona, Daniel Tordera and Henk J. Bolink|2013|J.Mater.Chem.C|1|2241|doi:10.1039/C3TC00808H
CCDC 968505: Experimental Crystal Structure Determination
Related Article: Filippo Monti, Florian Kessler, Manuel Delgado, Julien Frey, Federico Bazzanini, Gianluca Accorsi, Nicola Armaroli, Henk J. Bolink, Enrique Ortí, Rosario Scopelliti, Md. Khaja Nazeeruddin, and Etienne Baranoff|2013|Inorg.Chem.|52|10292|doi:10.1021/ic400600d
CCDC 968509: Experimental Crystal Structure Determination
Related Article: Filippo Monti, Florian Kessler, Manuel Delgado, Julien Frey, Federico Bazzanini, Gianluca Accorsi, Nicola Armaroli, Henk J. Bolink, Enrique Ortí, Rosario Scopelliti, Md. Khaja Nazeeruddin, and Etienne Baranoff|2013|Inorg.Chem.|52|10292|doi:10.1021/ic400600d