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. 2022 May:245:118768.
doi: 10.1016/j.jlumin.2022.118768. Epub 2022 Feb 4.

Carbazole-Functionalized Dipicolinato LnIII Complexes Show Two-Photon Excitation and Viscosity-Sensitive Metal-Centered Emission

Jorge H S K Monteiro  1   2 , Natalie R Fetto  1   3 , Matthew J Tucker  1 , Fernando A Sigoli  4 , Ana de Bettencourt-Dias  1
Affiliations

Carbazole-Functionalized Dipicolinato LnIII Complexes Show Two-Photon Excitation and Viscosity-Sensitive Metal-Centered Emission

Jorge H S K Monteiro et al. J Lumin. 2022 May.

Abstract

EuIII and YbIII complexes with the carbazole-dipicolinato ligand dpaCbz2-, namely K3[Eu(dpaCbz)3] and K3[Yb(dpaCbz)3], were isolated. The EuIII complex displayed metal-centred emission upon one-photon excitation with a sensitized emission efficiency Φ L Ln of 1.8±0.3 %, corresponding to an intrinsic emission efficiency Φ Ln Ln of 46% and a sensitization efficiency of ηsens 3.9%, with an emission lifetime of the emissive state τ of 1.087±0.005 ms. The YbIII complex displayed Φ L Ln of 0.010±0.001 %, and a τ of 2.32±0.06 μs. The EuIII-centred emission was sensitized as well upon two-photon excitation and a two-photon absorption cross-section σ2PA of 63 GM at 750 nm was determined for the complex. The one- or two-photon sensitized emission intensity of the EuIII complex changes by more than two-fold when the solvent viscosity is varied in the range 0.5 - 200 cP and the emission is independent of dissolved oxygen. The YbIII complex displays a change in emission intensity as well. However, in this case, a dependence of the emission intensity on dissolved oxygen content was observed.

Keywords: Europium; carbazole-functionalized dipicolinato; lanthanide luminescence; two-photon absorption; two-photon absorption cross-section; viscosity sensing; ytterbium.

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Conflict of interest statement

Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Figures

Figure 1.
Figure 1.
a) Modified Jablønski diagram of the antenna effect with one- (IPA) and two-photon (2PA) absorption. F designates fluorescence, P phosphorescence, ISC intersystem crossing, ET energy transfer, BT back-transfer, L luminescence, NR non-radiative pathways, and S states with singlet and T states with triplet multiplicity.[24] b) Structure of H2dpaCbz (carbazole moiety highlighted in red).
Figure 2.
Figure 2.
Emission spectra of the complex K3[Eu(dpaCbz)3] obtained at different laser powers. The inset shows the plot of log (I) as a function of log (P). [complex] = 0.2 mM in TRIS/HC1 buffered solution (4% DMSO, pH ~7.4).
Figure 3.
Figure 3.
(a) Emission spectra of K3[Eu(dpaCbz)3] (λexc = 380 nm) upon one-photon excitation with varying viscosities, (b) Emission spectra of K3[Eu(dpaCbz)3] (λexc = 720 nm) upon two-photon excitation with varying viscosities. The insets show the plot of the emission intensity at 615 nm as a function of viscosity, [complex] = 0.2 mM. Solutions with varying ratios of MeOH:glycerol were used with viscosity in the range 0.5 – 200 cP.
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