Enhanced Electric Dipole Transition in Lanthanide Complex with Organometallic Ruthenocene Units

Hasegawa, Yasuchika; Sato, Nao; Hirai, Yuichi; Nakanishi, Takayuki; Kitagawa, Yuichi; Kobayashi, Atsushi; Kato, Masako; Seki, Tomohiro; Ito, Hajime; Fushimi, Koji

doi:10.1021/acs.jpca.5b01809

Cited by 23 publications

(23 citation statements)

References 50 publications

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“…We reported luminescent Eu(III) complexes attached with ruthenocene units (Fig. 8j) 95 103,104 , and Os-Ln(III) 96 systems has also been reported. In general, their CT (MLCT, LMCT, metalmetal-to-ligand CT, etc.)…”

Section: Light and Transition Metal Complexessupporting

confidence: 53%

Effective photosensitized, electrosensitized, and mechanosensitized luminescence of lanthanide complexes

2018

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The 4f-4f emission of Tb(III), Eu(III), and Sm(III) complexes plays an important role in the design of monochromatic green, red, and deep-red luminescent materials for displays, lighting, and sensing devices. The 4f-4f emission of Yb(III), Nd(III), and Er(III) complexes is observed in the near-infrared (IR) region for bioimaging and security applications. However, their absorption coefficients are extremely small (ε < 10 L mol −1 cm −1 ). In this review, photosensitized luminescent lanthanide(III) complexes containing organic chromophores (ligands) with large absorption coefficients (ε > 10,000 L mol −1 cm −1 ) are introduced. Organic molecular design elements, including (1) the control of the excited triplet (T 1 ) state, (2) the effects on the charge-transfer (CT) band, and (3) the energy transfer from metal ions for effective photosensitized luminescence, are explained. The characteristic electrosensitized luminescence (electroluminescence) and mechanoluminescence (triboluminescence) of lanthanide(III) complexes are also explained. Lanthanide(III) complexes with well-designed organic molecules are expected to open avenues of research among the fields of chemistry, physics, electronics, and material science.

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Section: Light and Transition Metal Complexessupporting

confidence: 53%

Effective photosensitized, electrosensitized, and mechanosensitized luminescence of lanthanide complexes

2018

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“…Mason and co-workers proposed the "ligand polarization" theory of 4f-4f hypersensitivity, which describes the relationship between induced dipole moment and dynamic coupling in the Judd-Ofelt theory. [15] The effect on dipole moment of the ligand in an Ln III complex has also been reported, [16] and large dipole moment of the ligands should increase 4f-4f transition probability. The enhancement of F ff in Eu III coordination zippers might be caused by the larger magnitude of the dipole moment in bridging ligands.…”

Section: Angewandte Chemiementioning

confidence: 88%

Luminescent Europium(III) Coordination Zippers Linked with Thiophene‐Based Bridges

et al. 2016

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Novel Eu III coordination polymers [Eu(hfa)3(dpt)]n (dpt: 2,5-bis(diphenylphosphoryl)thiophene) and [Eu(hfa)3(dpedot)]n (dpedot: 2,5-bis(diphenylphosphoryl)ethylenedioxythiophene) with hydrogenbonded zipper structures are reported. The coordination polymers are composed of Eu III ions, hexafluoroacetylacetonato ligands, and thiophene-based phosphine oxide bridges. The zig-zag orientation of single polymer chains induced the formation of densely packed coordination structures with multiple intermolecular interactions, resulting in thermal stability above 300˚C. They exhibit a high intrinsic emission quantum yield (~ 80%) due to their asymmetrical and low-vibrational coordination structures around Eu III ions. In addition, the characteristic alternative orientation of substituents also contributes to the dramatically high ligand-to-metal energy transfer efficiencies of up to 80% in solid state.The development of luminescent molecular materials with high quantum efficiencies is required for applications in bioassays, light-emitting devices, and chemical and physical sensors. [1] There have been many reports on luminescent organic and coordination compounds. Swager and co-workers developed amplifying fluorescent conjugated polymers for biological and chemical sensors such as highly explosive trinitrotoluene in seawater. [2] Adachi et al. demonstrated very high phosphorescence efficiency of Ir III coordination compounds in organic light-emitting devices. [3] Among these materials, lanthanide coordination compounds are promising candidates for pure and strong luminophores due to their versatile photophysical properties derived from the 4f-4f transitions in lanthanide (Ln III ) ions. [4] Ln III ions, however, show small absorption coefficients (ε < 10 M -1 cm -1 ), and various organic chromophores such as β-diketonates and pyridinebased ligands have been developed to sensitize the luminescence of Ln III ions. [5] These organic compounds with π conjugation systems are referred to as light-harvesting antenna ligands. The overall emission quantum yields of Ln III compounds are described as ・・・ (1) where Φff is Ln III -centered emission quantum yield, ηsens is efficiency of the sensitization process, and kr and knr are radiative and nonradiative rate constants, respectively.Ln III coordination compounds with high Φff have been successfully synthesized by introducing asymmetric coordination structures, resulting in a large kr value. [6] In order to improve thermal and photophysical properties of Ln III compounds for optical applications, Ln III coordination polymers with rigid multidimensional networks have been developed over the past two decades. [7] The rigid coordination structures can also contribute to strong emission by suppressing a non-emissive process (knr) associated with vibrational relaxation.The antenna and bridging ligands in Ln III coordination polymers dominate their photophysical and thermodynamic properties. Bünzli and co-workers reported that Eu III coordination polymers with low-vibration...

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“…Increasing n increases the binding ability of (10) to lanthanide ions. [60]. This was rationalised as being due to repulsion of the positively charged ruthenocenyl cations formed leading to a change in geometry and offers potential in switchable photoluminescent devices.…”

Section: Complexes With Lanthanide B-diketonatesmentioning

confidence: 99%

Lanthanide phosphine oxide complexes

Platt

2017

Coordination Chemistry Reviews

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Phosphine oxide complexes of lanthanide metal have been studied to elucidate the fundamental aspects of their structural chemistry and to develop important technological applications mainly in the reprocessing of nuclear fuels and in photoluminescent devices but also in other fields such as gas sorption and homogeneous catalysis. The aim of this review is to give an overview of the range of complexes with phosphine oxides and trivalent lanthanide and yttrium ions, their structural features and applications.

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Enhanced Electric Dipole Transition in Lanthanide Complex with Organometallic Ruthenocene Units

Cited by 23 publications

References 50 publications

Effective photosensitized, electrosensitized, and mechanosensitized luminescence of lanthanide complexes

Effective photosensitized, electrosensitized, and mechanosensitized luminescence of lanthanide complexes

Luminescent Europium(III) Coordination Zippers Linked with Thiophene‐Based Bridges

Lanthanide phosphine oxide complexes

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