Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 1. Bis complexes of rhodium(III) and iridium(III)

Huang, Wen Liang; Segers, Donald P.; DeArmond, M. Keith

doi:10.1021/j150614a026

Cited by 28 publications

(5 citation statements)

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“…plexes, as the rigid matrix and the low temperature usually hinder the non-radiative mechanisms, thus increasing the luminescence intensity and the relevant excited-state lifetime. [1] While the mononuclear complexes exhibited lifetimes in the range of the microseconds, τ = 4.8 μs for 1 and τ = 5.2 μs for 2, which are in line with previous findings of other mononuclear Ir(III) complexes [29,31,41,55,[58][59][60][61], the binuclear complex 3 showed significantly longer emission lifetimes, in the range of the milliseconds: τ = 5.5 ms. As mentioned before, the extended conjugation and the presence of substituents on the ligands play a significant role in the photophysics of the complexes. It should be noted that relatively long lifetimes in the microseconds scale have been found in other families of binuclear Ir(III) complexes with different bridging ligands [31,[47][48][49][62][63][64][65], but excited state lifetimes in the millisecond scale are relatively rare for Ir(III) complexes [1].…”

Section: Luminescence Propertiessupporting

confidence: 91%

Rational Design of Mono- and Bi-Nuclear Cyclometalated Ir(III) Complexes Containing Di-Pyridylamine Motifs: Synthesis, Structure, and Luminescent Properties

et al. 2022

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Heteroleptic cyclometalated iridium (III) complexes (1–3) containing di-pyridylamine motifs were prepared in a stepwise fashion. The presence of the di-pyridylamine ligands tunes their electronic and optical properties, generating blue phosphorescent emitters at room temperature. Herein we describe the synthesis of the mononuclear iridium complexes [Ir(ppy)2(DPA)][OTf] (1), (ppy = phenylpyridine; DPA = Dipyridylamine) and [Ir(ppy)2(DPA-PhI)][OTf] (2), (DPA-PhI = Dipyridylamino-phenyliodide). Moreover, the dinuclear iridium complex [Ir(ppy)2(L)Ir(ppy)2][OTf]2 (3) containing a rigid angular ligand “L = 3,5-bis[4-(2,2′-dipyridylamino)phenylacetylenyl]toluene” and displaying two di-pyridylamino groups was also prepared. For comparison purposes, the related dinuclear rhodium complex [Rh (ppy)2(L)Rh(ppy)2][OTf]2 (4) was also synthesized. The x-ray molecular structure of complex 2 was reported and confirmed the formation of the target molecule. The rhodium complex 4 was found to be emissive only at low temperature; in contrast, all iridium complexes 1–3 were found to be phosphorescent in solution at 77 K and room temperature, displaying blue emissions in the range of 478–481 nm.

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Section: Luminescence Propertiessupporting

confidence: 91%

Rational Design of Mono- and Bi-Nuclear Cyclometalated Ir(III) Complexes Containing Di-Pyridylamine Motifs: Synthesis, Structure, and Luminescent Properties

et al. 2022

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“…Although there is no rigorous theoretical treatment available at present for the electronic spectra of tricobalt compounds, the origin of the transitions can be assigned tentatively by comparing the spectra with that of the ligand and mononuclear dpa complexes. The high-intensity band at 312 nm is similar to that displayed by the free ligand and is assigned as a spin-allowed π − π* transition. The shoulder at 369 nm is likely to be a charge-transfer band.…”

Section: Resultsmentioning

confidence: 73%

New Linear Tricobalt Complex of Di(2-pyridyl)amide (dpa), [Co₃(dpa)₄(CH₃CN)₂][PF₆]₂

et al. 2000

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Reaction of the linear tricobalt compound Co3(dpa)4Cl2 (1) (dpa = di(2-pyridyl)amide) with silver hexafluorophosphate in acetonitrile yields [Co3(dpa)4(CH3CN)2][PF6]2 (2). Two crystalline forms are obtained from the same solution, namely, a monoclinic (P2(1)) form 2xCH3CNx2Et2O and a triclinic (P1) form, 2x3CH3CN. The tricobalt units in both crystals are essentially symmetrical, though this is not required by crystal symmetry, with Co-Co distances in the range 2298-2304 A. Each of the two terminal Co atoms is coordinated to an acetonitrile molecule with Co-N distances in the range 2068-2111 A at 213 K. The spiral arrangement of ligands gives an overall idealized D4 point group symmetry for the cation [Co3(dpa)4(CH3CN)2]2+ . Chiral crystals of both delta and lambda configurations in the P2(1) form have been isolated. The absolute configurations were determined by X-ray crystallography and their mirror-image circular dichroism spectra measured. The D4 symmetry of the cation appears to be preserved in solution as judged by the presence of only five proton resonance signals in the 1H NMR spectrum. Magnetic susceptibility measurements in the solid state indicates that 2 has a doublet ground state and exhibits an increase of the effective moment at high temperature (approximately 160 K) due to a spin crossover process.

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“…[21][22][23] Iridium complexes generally exhibit phosphorescence through the excited triplet-state. 24,25) BTPHSA exhibited phosphorescence in the same way for typical iridium complexes.…”

Section: Resultsmentioning

confidence: 54%

Biological oxygen sensing via two-photon absorption by an Ir(III) complex using a femtosecond fiber laser

Moritomo¹,

Fujii²,

Suzuki³

et al. 2016

Jpn. J. Appl. Phys.

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Near-infrared two-photon absorption of the phosphorescent Ir(III) complex (2,4-pentanedionato-κO 2,κO 4)bis[2-(6-phenanthridinyl-κN)benzo[b]thien-3-yl-κC]iridium (BTPHSA) was characterized. It exhibited a 800–1200 nm two-photon absorption band, and thus could be electronically excited by 1030-nm femtosecond Ti:sapphire and Yb-doped fiber lasers. By using BTPHSA, oxygen concentrations in human embryonic kidney 293 (HEK293) cells were imaged. These results demonstrate two-photon oxygen sensing of live tissues via easily operable excitation sources.

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Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 1. Bis complexes of rhodium(III) and iridium(III)

Cited by 28 publications

References 0 publications

Rational Design of Mono- and Bi-Nuclear Cyclometalated Ir(III) Complexes Containing Di-Pyridylamine Motifs: Synthesis, Structure, and Luminescent Properties

Rational Design of Mono- and Bi-Nuclear Cyclometalated Ir(III) Complexes Containing Di-Pyridylamine Motifs: Synthesis, Structure, and Luminescent Properties

New Linear Tricobalt Complex of Di(2-pyridyl)amide (dpa), [Co₃(dpa)₄(CH₃CN)₂][PF₆]₂

Biological oxygen sensing via two-photon absorption by an Ir(III) complex using a femtosecond fiber laser

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Emission studies of transition-metal complexes of 2,2'-dipyridylamine. 1. Bis complexes of rhodium(III) and iridium(III)

Cited by 28 publications

References 0 publications

Rational Design of Mono- and Bi-Nuclear Cyclometalated Ir(III) Complexes Containing Di-Pyridylamine Motifs: Synthesis, Structure, and Luminescent Properties

Rational Design of Mono- and Bi-Nuclear Cyclometalated Ir(III) Complexes Containing Di-Pyridylamine Motifs: Synthesis, Structure, and Luminescent Properties

New Linear Tricobalt Complex of Di(2-pyridyl)amide (dpa), [Co3(dpa)4(CH3CN)2][PF6]2

Biological oxygen sensing via two-photon absorption by an Ir(III) complex using a femtosecond fiber laser

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New Linear Tricobalt Complex of Di(2-pyridyl)amide (dpa), [Co₃(dpa)₄(CH₃CN)₂][PF₆]₂