4f–5d Transitions of Tb3+ in Cs2NaYF6: The Effect of Distortion of the Excited-State Configuration

Duan, Chang‐Kui; Tanner, Peter A.; Meijerink, Andries; Makhov, V.N.

doi:10.1021/jp205011v

Cited by 22 publications

(12 citation statements)

References 19 publications

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“…It is rare that d-f emission spectra of lanthanides show such a well-resolved vibrational fine structure in which multiple vibrational modes can be identified. In previous work well-resolved spectra showing coupling with two vibrations have been reported for Ce 3+ , Pr 3+ and Tb 3+ in elpasolites [18][19][20] with values for S between 1 and 2.…”

Section: Luminescence Spectramentioning

confidence: 54%

Bright yellow and green Eu(ii) luminescence and vibronic fine structures in LiSrH3, LiBaH3 and their corresponding deuterides

Kunkel

Meijerink

Kohlmann

2014

Phys. Chem. Chem. Phys.

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The luminescence of Eu(2+) in hydride and deuteride perovskite hosts LiMH3 and LiMD3 (M = Sr, Ba) is reported. Bright yellow (M = Sr) and green (M = Ba) emission is observed and assigned to 4f(6)5d-4f(7) emission from Eu(2+) in the highly symmetric 12-coordinated M(2+) site (m3[combining macron]m). The long wavelength of the emission is explained by the strong covalence and crystal field splitting in europium's coordination by hydride anions. A well-resolved vibrational structure in the emission and excitation spectra of Eu(2+) in the Sr-compounds allows for an accurate determination of the energy of the lowest 4f(6)5d state and vibrational frequencies, for both the hydride and deuteride. The isotope effect on the energy of the fd states is small (∼70 cm(-1)), as expected. Surprisingly, also the vibrational energies observed in the vibronic progression are similar for the d-f emission spectra in LiSrH3 and LiSrD3. This is explained by strong coupling of the d-f emission with low energy acoustic phonons which, contrary to optical phonons, are not strongly affected by replacing H by D. The present results provide insight into the long wavelength Eu(2+) emission in hydride coordination and the influence of isotope replacement on the luminescence.

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Section: Luminescence Spectramentioning

confidence: 54%

Bright yellow and green Eu(ii) luminescence and vibronic fine structures in LiSrH3, LiBaH3 and their corresponding deuterides

Kunkel

Meijerink

Kohlmann

2014

Phys. Chem. Chem. Phys.

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“…Also in d 1 systems such as Al 2 O 3 :Ti 3+ 21 Jahn–Teller distortion of the ground and excited state has been reported, leading to spectra different from those predicted by the crystal‐field theory. For 4f5d states of lanthanides a Jahn–Teller distortion has been suggested, with a small (75 cm –1 ) Jahn–Teller stabilization energy 22. Normalized emission spectra of the single crystals for different temperatures are shown in Figure 4.…”

Section: Resultsmentioning

confidence: 99%

Green Luminescence of Divalent Europium in the Hydride Chloride EuHCl

Kunkel

Rudolph

Meijerink

et al. 2015

Zeitschrift anorg allge chemie

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Abstract. Luminescence properties of divalent europium in the mixedanion hydride chloride EuHCl were studied for the first time. Olivegreen single crystals of EuHCl (PbFCl-type structure: tetragonal, P4/nmm, a = 406.58(3) pm, c = 693.12(5) pm, c/a = 1.705, Z = 2) resulted from the reaction of elemental europium (Eu), sodium hydride (NaH) and sodium chloride (NaCl), while powder samples were prepared from the binary components europium dihydride (EuH 2 ) and dichloride (EuCl 2 ). Low temperature X-ray powder diffraction proved the absence of phase transitions for 12(2) K Յ T Յ 295(2) K. Bright green emission was observed under UV-excitation and assigned to the

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“…The position of the latter strongly depends on the coordination sphere. Unfortunately, no respective investigations of cyanide‐containing compounds are available, but for Cs 2 NaYF 6 :Tb 3+ 41 and BaGdB 9 O 16 :Tb 3+ 42 the f–d transition bands are located at energies above 280 nm. These bands can be attributed to excited states of the ligands.…”

Section: Resultsmentioning

confidence: 99%

Antenna‐ and Metal‐Triggered Luminescence in Dense 1,3‐Benzodinitrile Metal–Organic Frameworks _∞³[LnCl₃(1,3‐Ph(CN)₂)], Ln = Eu, Tb

et al. 2012

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Keywords: Metal-organic frameworks / Luminescence / Lanthanides / Antenna effect Luminescent homoleptic dense 1,3-benzodinitrile MOFs (metal-organic frameworks) of Eu 3+ and Tb 3+ were prepared from the anhydrous chlorides LnCl 3 (Ln = Eu, Tb) and a melt of the linker ligand 1,3-benzodinitrile [1,3-Ph(CN) 2 =C 6 H 4 -(CN) 2 ]. The 1,3-benzodinitrile ligands act as chemical scissors and cut down the LnCl 3 structure to 2D sheets of trigonal Cl ion prisms around the rare earth ions and interlinks these nets to form a 3D framework structure of the formula ϱ 3 [LnCl 3 (1,3-Ph(CN) 2 )]. Both compounds exhibit photoluminescence of the trivalent rare earth ions although they are fully concentrated (100 % luminescence centres), and are the sole examples in which a dinitrile linker is utilized as an antenna for rare earth luminescence subsequent to a transfer of the energy from an excited ligand state to an excited 4f state [a]

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4f–5d Transitions of Tb³⁺ in Cs₂NaYF₆: The Effect of Distortion of the Excited-State Configuration

Cited by 22 publications

References 19 publications

Bright yellow and green Eu(ii) luminescence and vibronic fine structures in LiSrH3, LiBaH3 and their corresponding deuterides

Bright yellow and green Eu(ii) luminescence and vibronic fine structures in LiSrH3, LiBaH3 and their corresponding deuterides

Green Luminescence of Divalent Europium in the Hydride Chloride EuHCl

Antenna‐ and Metal‐Triggered Luminescence in Dense 1,3‐Benzodinitrile Metal–Organic Frameworks _∞³[LnCl₃(1,3‐Ph(CN)₂)], Ln = Eu, Tb

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4f–5d Transitions of Tb3+ in Cs2NaYF6: The Effect of Distortion of the Excited-State Configuration

Cited by 22 publications

References 19 publications

Bright yellow and green Eu(ii) luminescence and vibronic fine structures in LiSrH3, LiBaH3 and their corresponding deuterides

Bright yellow and green Eu(ii) luminescence and vibronic fine structures in LiSrH3, LiBaH3 and their corresponding deuterides

Green Luminescence of Divalent Europium in the Hydride Chloride EuHCl

Antenna‐ and Metal‐Triggered Luminescence in Dense 1,3‐Benzodinitrile Metal–Organic Frameworks ∞3[LnCl3(1,3‐Ph(CN)2)], Ln = Eu, Tb

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4f–5d Transitions of Tb³⁺ in Cs₂NaYF₆: The Effect of Distortion of the Excited-State Configuration

Antenna‐ and Metal‐Triggered Luminescence in Dense 1,3‐Benzodinitrile Metal–Organic Frameworks _∞³[LnCl₃(1,3‐Ph(CN)₂)], Ln = Eu, Tb