Effects of alkyl groups in diphosphine dioxide-ligand for Eu(III)-β-diketonate complexes on photoluminescence properties

Iwanaga, Hiroki

doi:10.1016/j.cplett.2019.136794

Cited by 9 publications

(5 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Larger Φ ET in the solid state than in the solution state has also been reported for other Eu(III)-βdiketonate complexes with asymmetric diphosphine dioxide ligands. 25,26 In conclusion, both Φ Ln and Φ ET of complex 2 in solid state are much larger than in the solution state, resulting in larger Φ TOT in the solid state compared with that in the solution state (solution: Φ Ln 0.50, Φ ET 0.42, and Φ TOT 0.21 and solid: Φ Ln 0.74, Φ ET 0.47, and Φ TOT : 0.35).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Substitution of CF 3 groups in phenyl groups of diphosphine dioxides effectively enhances the solubility. , Thienyl-substituted diphosphine dioxide ligands serve to suppress the concentration quenching of Eu(III) complexes . Bulky alkyl groups in a diphosphine dioxide ligand increase the half widths of the 5 D 0 → 7 F 2 transition of Eu(III) complexes . The mutual positions of the nearest oxygen atoms around the Eu(III) ion can be strained by bulky substituents, which enhances Φ ET .…”

Section: Introductionmentioning

confidence: 99%

“…25 Bulky alkyl groups in a diphosphine dioxide ligand increase the half widths of the 5 D 0 → 7 F 2 transition of Eu(III) complexes. 26 The mutual positions of the nearest oxygen atoms around the Eu(III) ion can be strained by bulky substituents, which enhances Φ ET . On the other hand, the photoluminescence of Eu(III)-β-diketonate is drastically and rapidly quenched by coexisting 2,2dichlorovinyl dimethyl phosphate (organophosphorus pesticide, popular name dichlorvos) through reducing Φ ET .…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Quantum Yield and Photoluminescence Intensity Enhancement Effects of a Diphosphine Dioxide Ligand on a 6-Coordinate Eu(III)-β-Diketonate Complex with Low Luminescence

Iwanaga

Aiga

2020

ACS Omega

Self Cite

View full text Add to dashboard Cite

Tris{6,6,7,7,8,8,8-heptafluoro-1-[2-(9,9-dimethylfluorenyl)]-1,3-octanedionate} europium(III) (Eu(III)(hfod)3 1) was synthesized, which was designed to have low luminescence and a large absorption coefficient in order to elucidate the coordination effects of phosphine oxide ligands. The quantum yield (ΦTOT) and photoluminescence intensity of complex 1 were dramatically enhanced by coordinating a diphenyl-4-(dibutylphosphinyl)butyl phosphine oxide (DPDB) ligand, thanks to the increased intrinsic photoluminescence quantum yield of the lanthanide (ΦLn) and the increased energy transfer efficiency (ΦET) in the solution and solid states. In the solid state, there was no energy dissipation by solvent molecules. This excluded the steric shielding effects of the DPDB ligand and allowed the effects of the ligand field environment to be extracted. ΦLn and ΦET of complex 2 were much larger in the solid state than those in the solution state, resulting in larger ΦTOT (solution state: ΦLn 0.50, ΦET 0.42, and ΦTOT 0.21 and solid state: ΦLn 0.74, ΦET 0.47, and ΦTOT 0.35). Larger asymmetry ratios (ratio R) of Eu(III)(hfod)3(DPDB) 2 than those of complex 1 in the solution and solid states indicate that the ligand field of the Eu(III) ion becomes more asymmetric by coordination of the DPDB ligand. Density functional theory calculations showed that ΦLn and ΦET increased when the ligand field around the Eu(III) ion became more asymmetric. Based on these results, we propose a hypothesis on the enhancement of the photoluminescence intensity of 6-coordinated Eu(III)-β-diketonate by a DPDB ligand. When a DPDB ligand coordinates to a Eu(III) ion, the positions of the nearest oxygen atoms around the Eu(III) ion are shifted by steric repulsion and the relative positions of the nearest oxygen atoms are distorted. The distorted coordination environment induces asymmetry in the ligand field, increasing ΦLn and ΦET. ΦTOT is enhanced by the DPDB ligand because it is the product of ΦLn and ΦET. Photoluminescence intensity increases because of the enhanced ΦTOT.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Quantum Yield and Photoluminescence Intensity Enhancement Effects of a Diphosphine Dioxide Ligand on a 6-Coordinate Eu(III)-β-Diketonate Complex with Low Luminescence

Iwanaga

Aiga

2020

ACS Omega

Self Cite

View full text Add to dashboard Cite

show abstract

“…Relationships between molecular structures of diphosphine dioxide ligands and photoluminescence properties of Eu(III)-β-diketonates were investigated systematically and found that slight differences in the molecular substructure of phosphine oxide ligands has significant effects on properties of Eu(III)-β-diketonates. [38][39][40][41][42][43] On the other hand, many organophosphorus insecticides are expected to coordinate to a Eu(III) ion and affect the photoluminescence properties of Eu(III)-β-diketonates because their oxygen atoms of P=O groups are strong Lewis bases. These results indicate that photoluminescence properties of Eu(III)-β-diketonates are changed by organophosphorus insecticides.…”

Section: Introductionmentioning

confidence: 99%

A simple and sensitive detection method for the pesticide dichlorvos in solution using Eu(III)-β-diketonate as a luminescent probe

Iwanaga

Aiga

2019

Jpn. J. Appl. Phys.

Self Cite

View full text Add to dashboard Cite

We developed a novel detection method for the pesticide dichlorvos (2,2-dichlorovinyl dimethyl phosphate) in which tris[4,4,5,5,6,6,6-heptafluoro-1-(2-naphthyl)-1,3-hexanedionato]europium(III) [Eu(III)(hfnh)3] served as a highly sensitive luminescent probe. The photoluminescence intensity of Eu(III)(hfnh)3 was drastically and rapidly decreased by the action of dichlorvos in ethyl acetate. The quantum yield of Eu(III)(hfnh)3 decreased monotonically with increasing dichlorvos concentration, explaining the decrease in photoluminescence intensity. Dynamic and static quenching mechanisms possibly co-existed in ethyl acetate because the Stern–Volmer plot of Eu(III)(hfnh)3 and dichlorvos could be approximated by a quadratic function. 31P-NMR revealed that dichlorvos molecules coordinated to Eu(III) and exhibited dynamic behavior supporting a dynamic quenching mechanism. When dichlorvos was mixed with Eu(III)(hfnh)3 1, ΦET drastically decreased from 0.64 to 0.15. A plausible mechanism is that quenching of Eu(III)(hfnh)3 1 occurred between the dichlorvos molecules and the β-diketonates before energy transfer from the β-diketonates to Eu(III). Density functional theory calculations support this mechanism.

show abstract

“…[25].Eu(III)(fod) 3 (DPDiPPBPO) has i-propyl groups in a diphosphine dioxide ligand, while Eu(III)(fod) 3 (DPDBPBPO) and Eu(III)(fod) 3 (DMPDBPBPO) have n-butyl groups.…”

mentioning

confidence: 99%

Photoluminescence Properties of Eu(III) Complexes with Two Different Phosphine Oxide Structures and Their Potential uses in Micro-LEDs, Security, and Sensing Devices: A Review

Iwanaga¹

2023

Adv. sci. technol. eng. syst. j.

Self Cite

View full text Add to dashboard Cite

In the field of micro-LED displays, there is strong demand for red phosphors with high photoluminescence intensity, high color purity, and small particle size. Here, we focus on Eu(III) complexes because they produce sharp photoluminescence spectra with high color purity and can be dissolved in polymer, enabling a reduction in particle size to the molecular level. We have previously established novel molecular design concepts for Eu(III) complexes by coordinating two different phosphine oxide structures to one Eu(III) ion in order to enhance photoluminescence intensity and increase solubility in polymers and solvents. Many Eu(III) complexes have been developed based on these concepts and their photoluminescence properties investigated. Eu(III) complexes with two different phosphine oxide structures are important candidates for red phosphors in micro-LEDs.

show abstract

Effects of alkyl groups in diphosphine dioxide-ligand for Eu(III)-β-diketonate complexes on photoluminescence properties

Cited by 9 publications

References 32 publications

Quantum Yield and Photoluminescence Intensity Enhancement Effects of a Diphosphine Dioxide Ligand on a 6-Coordinate Eu(III)-β-Diketonate Complex with Low Luminescence

Quantum Yield and Photoluminescence Intensity Enhancement Effects of a Diphosphine Dioxide Ligand on a 6-Coordinate Eu(III)-β-Diketonate Complex with Low Luminescence

A simple and sensitive detection method for the pesticide dichlorvos in solution using Eu(III)-β-diketonate as a luminescent probe

Photoluminescence Properties of Eu(III) Complexes with Two Different Phosphine Oxide Structures and Their Potential uses in Micro-LEDs, Security, and Sensing Devices: A Review

Contact Info

Product

Resources

About