0000000001304287
AUTHOR
Jennifer A. Zampese
Efficient Green Light-Emitting Electrochemical Cells Based on Ionic Iridium Complexes with Sulfone-Containing Cyclometalating Ligands
A new approach to obtain green-emitting iridiumA complexes is described. The synthetic approach consists of introducing a methylsulfone electron-withdrawing substituent into a 4-phenylpyrazole cyclometalating ligand in order to stabilize the highest- occupied molecular orbital (HOMO). Six new complexes have been synthe- sized incorporating the conjugate base of 1-(4-(methylsulfonyl)phenyl)-1 H- pyrazole as the cyclometalating ligand. The complexes show green emission and very high photoluminescence quantum yields in both diluted and concentrated films. When used as the main active component in light-emit- ting electrochemical cells (LECs), green electroluminance is observed. High efficienci…
Thienylpyridine-based cyclometallated iridium(III) complexes and their use in solid state light-emitting electrochemical cells
The synthesis and characterization of four iridium(iii) complexes [Ir(thpy)2(N^N)][PF6] where Hthpy = 2-(2'-thienyl)pyridine and N^N are 6-phenyl-2,2'-bipyridine (1), 4,4'-di-(t)butyl-2,2'-bipyridine (2), 4,4'-di-(t)butyl-6-phenyl-2,2'-bipyridine (3) or 4,4'-dimethylthio-2,2'-bipyridine (4) are described. The single crystal structures of ligand 4 and the complexes containing the [Ir(thpy)2(1)](+) and [Ir(thpy)2(4)](+) cations have been determined. In [Ir(thpy)2(1)](+), the pendant phenyl ring engages in an intra-cation π-stacking interaction with one of the thienyl rings in the solid state, and undergoes hindered rotation on the NMR timescale in [Ir(thpy)2(1)](+) and [Ir(thpy)2(3)](+). The …
Solution, structural and photophysical aspects of substituent effects in the N^N ligand in [Ir(C^N)2(N^N)]+ complexes
The syntheses and properties of a series of eleven new [Ir(ppy)2(N^N)][PF6] complexes (Hppy = 2-phenylpyridine) are reported. The N^N ligands are based on 2,2-bipyridine (bpy), substituted in the 6- or 5-positions with groups that are structurally and electronically diverse. All but two of the N^N ligands incorporate an aromatic ring, designed to facilitate intra-cation face-to-face π-interactions between the N^N and one [ppy](-) ligand. Within the set of ligands, 6-(3-tolyl)-2,2'-bipyridine (5), 4,6-bis(4-nitrophenyl)-2,2'-bipyridine (9), and 4,6-bis(3,4,5-trimethoxyphenyl)-2,2'-bipyridine (10) are new and their characterization includes single crystal structures of 9, and two polymorphs o…
Bright and stable light-emitting electrochemical cells based on an intramolecularly π-stacked, 2-naphthyl-substituted iridium complex
The synthesis and characterization of a new cationic bis-cyclometallated iridium(III) complex and its use in solid-state light-emitting electrochemical cells (LECs) are described. The complex [Ir(ppy)2(Naphbpy)][PF6], where Hppy = 2-phenylpyridine and Naphbpy = 6-(2-naphthyl)-2,2′-bipyridine, incorporates a pendant 2-naphthyl unit that π-stacks face-to-face with the adjacent ppy− ligand and acts as a peripheral bulky group. The complex presents a structureless emission centred around 595–600 nm both in solution and in thin film with relatively low photoluminescence quantum yields compared with analogous systems. Density functional theory calculations support the charge transfer character of…
Copper(i) complexes for sustainable light-emitting electrochemical cells
Four prototype heteroleptic copper(I) complexes [Cu(bpy)(pop)][PF6] (bpy = 2,2′-bipyridine, pop = bis(2-(diphenylphosphino)phenyl)ether), [Cu(phen)(pop)][PF6] (phen = 1,10-phenanthroline), [Cu(bpy)(pdpb)][PF6] (pdpb = 1,2-bis(diphenylphosphino)benzene) and [Cu(phen)(pdpb)][PF6] are presented. The synthesis, X-ray structures, solution and solid-state photophysical studies, and the performance in light-emitting electrochemical cells (LECs) of these complexes are described. Their photophysical properties are interpreted with the help of density functional theory (DFT) calculations. The photophysical studies in solution and in the solid-state indicate that these copper(I) complexes show good lu…
Red emitting [Ir(C^N)2(N^N)]+ complexes employing bidentate 2,2':6,2''-terpyridine ligands for light-emitting electrochemical cells
2,2':6',2''-Terpyridine (tpy), 4'-(4-HOC6H4)-2,2':6',2''-terpyridine (1), 4'-(4-MeOC6H4)-2,2':6',2''-terpyridine (2), 4'-(4-MeSC6H4)-2,2':6',2''-terpyridine (3), 4'-(4-H2NC6H4)-2,2':6',2''-terpyridine (4) and 4'-(4-pyridyl)-2,2':6',2''-terpyridine (4) act as N^N chelates in complexes of the type [Ir(C^N)2(N^N)][PF6] in which the cyclometallating ligand, C^N, is derived from 2-phenylpyridine (Hppy) or 3,5-dimethyl-1-phenyl-1H-pyrazole (Hdmppz). The single crystal structures of eight complexes have been determined, and in each iridium(III) complex cation, the non-coordinated pyridine ring of the tpy unit is involved in a face-to-face π-stacking interaction with the cyclometallated ring of an …
Tuning the photophysical properties of cationic iridium(iii) complexes containing cyclometallated 1-(2,4-difluorophenyl)-1H-pyrazole through functionalized 2,2′-bipyridineligands: blue but not blue enough
Four new heteroleptic iridium(III) complexes in the family [Ir(dfppz)(2)((NN)-N-boolean AND)](+), where Hdfppz = 1-(2,4-difluorophenyl)-1H-pyrazole and (NN)-N-boolean AND = 6-phenyl-2,2'-bipyridine (1), 4,4'-(di-tert-butyl)-6-phenyl-2,2'-bipyridine (2), 4,4'-(di-tert-butyl)-6,6'-diphenyl-2,2'-bipyridine (3) and 4,4'-bis(dimethylamino)-2,2'-bipyridine (4), have been synthesized as the hexafluoridophosphate salts and fully characterized. Single crystal structures of ligand 3 and the precursor [Ir-2(dfppz)(4)(mu-Cl)(2)] have been determined, along with the structures of the complexes 4{[Ir(dfppz)(2)(1)][PF6]}center dot 3CH(2)Cl(2), [Ir(dfppz)(2)(3)][PF6]center dot CH2Cl2 and [Ir(dfppz)(2)(4)][…
Fine‐Tuning of Photophysical and Electronic Properties of Materials for Photonic Devices Through Remote Functionalization
We report four new iridium(III) complexes of the type [Ir(ppy)2(N?N)][PF6] in which N?N is a 4,6-diphenyl-2,2`-bipyridine and the 4-phenyl ring is substituted at either the para or meta positions [4-Me, N?N = 1; 4-Br, N?N = 2; 3,5-Br2, N?N = 3; 3,5-(C6H4-4-NPh2)2, N?N = 4]. The complexes have been fully characterized, and single-crystal diffraction analyses of [Ir(ppy)2(N?N)][PF6] (N?N = 13) confirmed that each [Ir(ppy)2(N?N)]+ cation exhibits face-to-face p-stacking between the pendant phenyl substituent of the N?N ligand and the cyclometallated phenyl ring of an adjacent [ppy] ligand. In solution, the complexes are short-lived emitters; the emission maxima for [Ir(ppy)2(1)][PF6], [Ir(ppy)…
Chloride ion impact on materials for light-emitting electrochemical cells
Small quantities of Cl(-) ions result in dramatic reductions in the performance of ionic transition metal complexes in light-emitting electrochemical cells. Strong ion-pairing between aromatic protons and chloride has been established in both the solid state and solution. X-ray structural determination of 2{[Ir(ppy)2(bpy)][Cl]}·2CH2Cl2·[H3O]·Cl reveals the unusual nature of an impurity encountered in the preparation of [Ir(ppy)2(bpy)][PF6].
Exceptionally long-lived light-emitting electrochemical cells: multiple intra-cation π-stacking interactions in [Ir(C^N)2(N^N)][PF6] emitters
A series of cyclometalated iridium(iii) complexes [Ir(C^N)2(N^N)][PF6] (N^N = 2,2′-bipyridine (1), 6-phenyl-2,2′-bipyridine (2), 4,4′-di-tert-butyl-2,2′-bipyridine (3), 4,4′-di-tert-butyl-6-phenyl-2,2′-bipyridine (4); HC^N = 2-(3-phenyl)phenylpyridine (HPhppy) or 2-(3,5-diphenyl)phenylpyridine (HPh2ppy)) are reported. They have been synthesized using solvento precursors so as to avoid the use of chlorido-dimer intermediates, chloride ion contaminant being detrimental to the performance of [Ir(C^N)2(N^N)][PF6] emitters in light-electrochemical cell (LEC) devices. Single crystal structure determinations and variable temperature solution 1H NMR spectroscopic data confirm that the pendant pheny…
CCDC 974016: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Catherine E. Housecroft, Gabriel E. Schneider, Jennifer A. Zampese, Henk J. Bolink, Antonio Pertegás, Cristina Roldan-Carmona|2014|Dalton Trans.|43|4653|doi:10.1039/C3DT53477D
CCDC 974019: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Catherine E. Housecroft, Gabriel E. Schneider, Jennifer A. Zampese, Henk J. Bolink, Antonio Pertegás, Cristina Roldan-Carmona|2014|Dalton Trans.|43|4653|doi:10.1039/C3DT53477D
CCDC 972526: Experimental Crystal Structure Determination
Related Article: Gabriel E. Schneider, Antonio Pertegás, Edwin C. Constable, Catherine E. Housecroft, Nik Hostettler, Collin D. Morris, Jennifer A. Zampese, Henk J. Bolink, José M. Junquera-Hernández, Enrique Ortí, Michele Sessolo|2014|J.Mater.Chem.C|2|7047|doi:10.1039/C4TC01171F
CCDC 1019228: Experimental Crystal Structure Determination
Related Article: Andreas M. Bünzli, Edwin C. Constable, Catherine E. Housecroft, Alessandro Prescimone, Jennifer A. Zampese, Giulia Longo, Lidón Gil-Escrig, Antonio Pertegás, Enrique Ortí, Henk J. Bolink|2015|Chemical Science|6|2843|doi:10.1039/C4SC03942D
CCDC 871500: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Markus Neuburger, Pirmin Rösel, Gabriel E. Schneider, Jennifer A. Zampese, Catherine E. Housecroft, Filippo Monti, Nicola Armaroli, Rubén D. Costa, and Enrique Ortí|2013|Inorg.Chem.|52|885|doi:10.1021/ic302026f
CCDC 974020: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Catherine E. Housecroft, Gabriel E. Schneider, Jennifer A. Zampese, Henk J. Bolink, Antonio Pertegás, Cristina Roldan-Carmona|2014|Dalton Trans.|43|4653|doi:10.1039/C3DT53477D
CCDC 949190: Experimental Crystal Structure Determination
Related Article: Andreas M. Bünzli, Henk J. Bolink, Edwin C. Constable, Catherine E. Housecroft, José M. Junquera-Hernández, Markus Neuburger, Enrique Ortí, Antonio Pertegás, Juan J. Serrano-Pérez, Daniel Tordera, Jennifer A. Zampese|2014|Dalton Trans.|43|738|doi:10.1039/C3DT52622D
CCDC 910854: Experimental Crystal Structure Determination
Related Article: Daniel Tordera, Andreas M. Bünzli, Antonio Pertegás, José M. Junquera-Hernández, Edwin C. Constable, Jennifer A. Zampese, Catherine E. Housecroft, Enrique Ortí, Henk J. Bolink|2013|Chem.-Eur.J.|19|8597|doi:10.1002/chem.201300457
CCDC 959828: Experimental Crystal Structure Determination
Related Article: Gabriel E. Schneider, Henk J. Bolink, Edwin C. Constable, Cathrin D. Ertl, Catherine E. Housecroft, Antonio Pertegàs, Jennifer A. Zampese, Andreas Kanitz, Florian Kessler, Sebastian B. Meier|2014|Dalton Trans.|43|1961|doi:10.1039/C3DT53229A
CCDC 871501: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Markus Neuburger, Pirmin Rösel, Gabriel E. Schneider, Jennifer A. Zampese, Catherine E. Housecroft, Filippo Monti, Nicola Armaroli, Rubén D. Costa, and Enrique Ortí|2013|Inorg.Chem.|52|885|doi:10.1021/ic302026f
CCDC 1019229: Experimental Crystal Structure Determination
Related Article: Andreas M. Bünzli, Edwin C. Constable, Catherine E. Housecroft, Alessandro Prescimone, Jennifer A. Zampese, Giulia Longo, Lidón Gil-Escrig, Antonio Pertegás, Enrique Ortí, Henk J. Bolink|2015|Chemical Science|6|2843|doi:10.1039/C4SC03942D
CCDC 949192: Experimental Crystal Structure Determination
Related Article: Andreas M. Bünzli, Henk J. Bolink, Edwin C. Constable, Catherine E. Housecroft, José M. Junquera-Hernández, Markus Neuburger, Enrique Ortí, Antonio Pertegás, Juan J. Serrano-Pérez, Daniel Tordera, Jennifer A. Zampese|2014|Dalton Trans.|43|738|doi:10.1039/C3DT52622D
CCDC 1019226: Experimental Crystal Structure Determination
Related Article: Andreas M. Bünzli, Edwin C. Constable, Catherine E. Housecroft, Alessandro Prescimone, Jennifer A. Zampese, Giulia Longo, Lidón Gil-Escrig, Antonio Pertegás, Enrique Ortí, Henk J. Bolink|2015|Chemical Science|6|2843|doi:10.1039/C4SC03942D
CCDC 974017: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Catherine E. Housecroft, Gabriel E. Schneider, Jennifer A. Zampese, Henk J. Bolink, Antonio Pertegás, Cristina Roldan-Carmona|2014|Dalton Trans.|43|4653|doi:10.1039/C3DT53477D
CCDC 974022: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Catherine E. Housecroft, Gabriel E. Schneider, Jennifer A. Zampese, Henk J. Bolink, Antonio Pertegás, Cristina Roldan-Carmona|2014|Dalton Trans.|43|4653|doi:10.1039/C3DT53477D
CCDC 974021: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Catherine E. Housecroft, Gabriel E. Schneider, Jennifer A. Zampese, Henk J. Bolink, Antonio Pertegás, Cristina Roldan-Carmona|2014|Dalton Trans.|43|4653|doi:10.1039/C3DT53477D
CCDC 974023: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Catherine E. Housecroft, Gabriel E. Schneider, Jennifer A. Zampese, Henk J. Bolink, Antonio Pertegás, Cristina Roldan-Carmona|2014|Dalton Trans.|43|4653|doi:10.1039/C3DT53477D
CCDC 949191: Experimental Crystal Structure Determination
Related Article: Andreas M. Bünzli, Henk J. Bolink, Edwin C. Constable, Catherine E. Housecroft, José M. Junquera-Hernández, Markus Neuburger, Enrique Ortí, Antonio Pertegás, Juan J. Serrano-Pérez, Daniel Tordera, Jennifer A. Zampese|2014|Dalton Trans.|43|738|doi:10.1039/C3DT52622D
CCDC 971737: Experimental Crystal Structure Determination
Related Article: Gabriel E. Schneider, Henk J. Bolink, Edwin C. Constable, Cathrin D. Ertl, Catherine E. Housecroft, Antonio Pertegàs, Jennifer A. Zampese, Andreas Kanitz, Florian Kessler, Sebastian B. Meier|2014|Dalton Trans.|43|1961|doi:10.1039/C3DT53229A
CCDC 974018: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Catherine E. Housecroft, Gabriel E. Schneider, Jennifer A. Zampese, Henk J. Bolink, Antonio Pertegás, Cristina Roldan-Carmona|2014|Dalton Trans.|43|4653|doi:10.1039/C3DT53477D
CCDC 871502: Experimental Crystal Structure Determination
Related Article: Edwin C. Constable, Markus Neuburger, Pirmin Rösel, Gabriel E. Schneider, Jennifer A. Zampese, Catherine E. Housecroft, Filippo Monti, Nicola Armaroli, Rubén D. Costa, and Enrique Ortí|2013|Inorg.Chem.|52|885|doi:10.1021/ic302026f
CCDC 1019227: Experimental Crystal Structure Determination
Related Article: Andreas M. Bünzli, Edwin C. Constable, Catherine E. Housecroft, Alessandro Prescimone, Jennifer A. Zampese, Giulia Longo, Lidón Gil-Escrig, Antonio Pertegás, Enrique Ortí, Henk J. Bolink|2015|Chemical Science|6|2843|doi:10.1039/C4SC03942D