CCC–Pincer–NHC Osmium Complexes: New Types of Blue-Green Emissive Neutral Compounds for Organic Light-Emitting Devices (OLEDs)

Alabau, Roberto G.; Eguillor, Beatriz; Esler, J.; Esteruelas, Miguel A.; Oliván, Montserrat; Oñate, Enrique; Tsai, Jui‐Yi; Xia, Chao

doi:10.1021/om500905t

Cited by 78 publications

(45 citation statements)

References 142 publications

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“…1 H NMR (300 MHz, CD2Cl2, 298 K): δ 9.05 (d, 3 JH-H = 6.3, 1 H, CHarom), 8.56 (d, 3 JH-H = 8.4, 1 H, CHarom), 7.92 (dd, 3 JH-H = 6.0, 3 JH-H = 1.5, 1 H, CHarom), 7.55 (d, 3 JH-H = 8.0, 1 H, CHarom), 7.35 (t, 3 JH-H = 7.6, 1 H, CHarom), 7.30 (dt, 3 JH-H = 7.5, 1 JH-H = 1.0, 1 H, CHarom), 7.16 (dt, 3 JH-H = 7.4, 1 JH-H = 0.8, 1 H, CHarom), 7.11 (t, 3 JH-H = 8.1, 1 H, CHarom), 6.63 (d, 3 JH-H = 7.3, 1 H, CHarom), 6.26 (d, 3 JH-H = 7.4, 1 H, CHarom), 2.54 (s, 3 H, py-CH3), 2.23 (s, 3 H, py-CH3), 1.89 (m, 6 H, PCH), 0.87 (dvt, JH-H = 6.8,N = 12.8,36 H,PCH(CH3)2), -12.06 (br, 3 H, OsH). 1 H NMR (300 MHz, CD2Cl2, 193 K): δ -10.68 (d,1 H),.1), -13.89 (d,.1). T1(min) (ms, OsH, 300 MHz, CD2Cl2, 203 K): 91 (-10.68 ppm).…”

Section: Methodsmentioning

confidence: 99%

Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion

et al. 2018

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A novel type of catalyst precursors for the dehydrogenation of hydrogen carriers based on organic liquids has been discovered. Complexes OsH6(P i Pr3)2 (1) and OsH(OH)(CO)(P i Pr3)2 (2) react with 1,3-bis(6'-methyl-2'-pyridylimino)isoindoline (HBMePI) to give OsH3{κ 2-Npy,Nimine-(BMePI)}(P i Pr3)2 (3) and OsH{κ 2-Npy,Nimine-(BMePI)}(CO)(P i Pr3)2 (4). The unprecedented  2-Npy,Nimine coordination mode of BMePI is thermodynamically preferred with Os(IV) and Os(II) metal fragments and allows to prepare BMePI-based dinuclear metal cations. Treatment of OsH2Cl2(P i Pr3)2 (5) with 0.5 equiv of HBMePI in the presence of KO t Bu affords the chloride salt of the bis(osmium(IV)) dinuclear cation [{OsH3(P i Pr3)2}2{-( 2-Npy,Nimine)2-BMePI}] + (6). Related homoleptic bis(osmium(II)) complexes have been also synthetized. Complex 4 reacts with the bis(solvento) [OsH(CO){ 1-O-[OCMe2]2}(P i Pr3)2]BF4 to give [{OsH(CO)(P i Pr3)2}2{-( 2-Npy,Nimine)2-BMePI}]BF4 (7), whereas the addition of 0.5 equiv of HBMePI to {OsCl( 6-C6H6)}2(-Cl)2 (8) affords [{OsCl( 6-C6H6)}2{-(κ 2-Npy,Nimine)2-BMePI}]Cl (9). The reactions of 4 with 8 and {OsCl( 6-p-cymene)}2(-Cl)2 (10) lead to the heteroleptic cations [(P i Pr3)2(CO)HOs{-( 2-Npy,Nimine)2-BMePI}OsCl( 6-arene)] + (arene = C6H6 (11), p-cymene (12)). The electronic structrure and electrochemical properties of the dinuclear complexes were also studied. Complexes 3 and 4 are efficient catalyst precursors for the acceptorless and base-free dehydrogenation of secondary and primary alcohols and cyclic and lineal amines. The primary alcohols afford aldehydes. The amount of H2 released per gram of heterocycle depends upon: the presence of a methyl group adjacent to the nitrogen atom, the position of the nitrogen atom in the heterocycle, and the size of the heterocycle.

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Section: Methodsmentioning

confidence: 99%

Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion

et al. 2018

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“…Recently, Whittle and Williams, Haga and co‐workers, De Cola and co‐workers, and Esteruelas and co‐workers have independently conducted studies on emitters bearing two tridentate chelates; namely bis‐tridentate metal complexes. This class of molecular designs is expected to be more robust and should be of higher efficiency attributed to the concomitant higher rigidity versus the traditional design bearing three bidentate chelates .…”

Section: Methodsmentioning

confidence: 99%

Bis‐Tridentate Ir(III) Metal Phosphors for Efficient Deep‐Blue Organic Light‐Emitting Diodes

et al. 2017

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which the developments still lag behind the green and red counterparts due to the intrinsically wider energy gaps. [2] Efficient blue-emitters are expected to reduce power consumption and improve color gamut; therefore, they have emerged as one paradigm of the full-color OLED displays and solid-state lighting. [3] Among the various known blue phosphors, the sky-blue emitter FIrpic is considered to be the archetypal design; hence, its modulation is at the forefront of modern research in OLEDs. [4] OLEDs made with FIrpic typically have Commission Internationale de l'Eclairage (CIE (x,y) ) coordinates of (0.17, 0.34) which is far from the National Television Standards Committee pure blue values of (0.14, 0.08). Progress with blue phosphors is further complicated by other issues, such as chemical and physical stabilities, emission quantum yield, and relative radiative lifetime. Moreover, almost all reports of decent blue phosphors were focused on the so-called tris-bidentate architectures, i.e., with either three bidentate cyclometalates of higher ligand-centered ππ* energy gap or two of these cyclometalate plus a third bidentate ancillary. [5] However, these complexes suffer from possible chelate dissociation upon excitation, giving inferior device performances and longevity. [6] Recently, Whittle and Williams, [7] Haga and co-workers, [8] De Cola and co-workers, [9] and Esteruelas and co-workers [10] have independently conducted studies on emitters bearing two tridentate chelates; namely bis-tridentate metal complexes. This class of molecular designs is expected to be more robust and should be of higher efficiency attributed to the concomitant higher rigidity versus the traditional design bearing three bidentate chelates. [11] Despite the obvious advantages, these associated studies were greatly hampered by the lack of systematic syntheses and poor performances on OLEDs. These difficulties were recently solved by proper selection of chelates to give the charge-neutral architecture [12] and the installment of a higher field strength coordination unit. [13] One known bis-tridentate metal complex is the sky-blue Ir(III) phosphor [Ir(mimf)(pzpyph F )] (SB = "sky-blue"), [14] where the tridentate 6-pyrazolyl-2-phenylpyridine (pzpyph F ) and pincer dicarbene chelate (mimf) act as the chromophoric and ancillary chelates, respectively (Scheme 1). These ligands control the emission color and give the greater ligand field strength needed for the efficient phosphors. [15] Hence, the OLED derived from SB gave maximum external quantum efficiency (max. EQE) of 27% and EQE of 24% at the practical Emissive Ir(III) metal complexes possessing two tridentate chelates (bis-tridentate) are known to be more robust compared to those with three bidentate chelates (tris-bidentate). Here, the deep-blue-emitting, bis-tridentate Ir(III) metal phosphors bearing both the dicarbene pincer ancillary such as 2,6-diimidazolylidene benzene and the 6-pyrazolyl-2-phenoxylpyridine chromophoric chelate are synthesized. A deep-blue organic light-em...

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“…[16] However,n eutralc ompounds seem to be better emittersf or device fabrication. [17] Thus, molecular iridium(III) derivatives are arousing more interest than iridium(III) salts. Most studies have focused on complexes containing two or three bidentate ligands.…”

Section: Introductionmentioning

confidence: 99%

η¹‐Arene Complexes as Intermediates in the Preparation of Molecular Phosphorescent Iridium(III) Complexes

Esteruelas

Gómez-Bautista

López

et al. 2017

Chemistry A European J

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Molecular phosphorescent heteroleptic bis-tridentate iridium(III) emitters have been prepared via η -arene intermediates. In the presence of 4.0 mol of AgOTf, the complex [(IrCl{κ -N,C,N-(pyC HMe py)})(μ-Cl)] (1; pyC H Me py=1,3-di(2-pyridyl)-4,6-dimethylbenzene) reacted with 9-(6-phenylpyridin-2-yl)-9H-carbazole (PhpyCzH) and 2-phenoxy-6-phenylpyridine (PhpyOPh) to give [Ir{κ -N,C,N-(pyC HMe py)}{κ -C,N,C'-(C H pyCzH)}]OTf (2) and [Ir{κ -N,C,N-(pyC HMe py)}{κ -C,N,C'-(C H pyOPh)}]OTf (3). The X-ray diffraction structures of 2 and 3 reveal that the carbazolyl and phenoxy substituents of the C,N,C' ligand coordinate to the metal center to form an η -arene π bond. Treatment of 2 and 3 with KOtBu led to the deprotonation of the coordinated carbon atom of the η -arene group to afford the molecular phosphorescent [5t+4t'] heteroleptic iridium(III) complexes [Ir{κ -N,C,N-(pyC HMe py)}{κ -C,N,C'-(C H pyCz)}] (4) and [Ir{κ -N,C,N-(pyC HMe py)}{κ -C,N,C'-(C H pyOC H )}] (5). These complexes are green emitters that display short lifetimes and high quantum yields of 0.73 (4) and 0.87 (5) in the solid state.

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CCC–Pincer–NHC Osmium Complexes: New Types of Blue-Green Emissive Neutral Compounds for Organic Light-Emitting Devices (OLEDs)

Cited by 78 publications

References 142 publications

Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion

Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion

Bis‐Tridentate Ir(III) Metal Phosphors for Efficient Deep‐Blue Organic Light‐Emitting Diodes

η¹‐Arene Complexes as Intermediates in the Preparation of Molecular Phosphorescent Iridium(III) Complexes

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CCC–Pincer–NHC Osmium Complexes: New Types of Blue-Green Emissive Neutral Compounds for Organic Light-Emitting Devices (OLEDs)

Cited by 78 publications

References 142 publications

Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion

Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion

Bis‐Tridentate Ir(III) Metal Phosphors for Efficient Deep‐Blue Organic Light‐Emitting Diodes

η1‐Arene Complexes as Intermediates in the Preparation of Molecular Phosphorescent Iridium(III) Complexes

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η¹‐Arene Complexes as Intermediates in the Preparation of Molecular Phosphorescent Iridium(III) Complexes