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Excitation-Wavelength-Dependent Luminescence of Chemically and Physically Mixed Europium and Terbium Phosphonates: Color-Tunable Luminescence, Near-White-Light Emission, and Selective Fe 3+ Detection.

Zhi-Jia HuMeng-Jung TsaiYi-Jung TuJing-Yun Wu
Published in: Chemistry (Weinheim an der Bergstrasse, Germany) (2023)
Molecular lanthanide phosphonates [Ln 2 (H 3 tpmm) 2 (H 2 O) 6 ] ⋅ xH 2 O (Ln=Eu, EuP; Ln=Tb, TbP) were synthesized. Single-crystal X-ray diffraction confirmed that EuP has a sandwich-like dinuclear structure, in which the Eu(III) center adopts a {EuO 8 } distorted dodecahedral geometry. XRPD patterns prove that TbP and EuP are isomorphous and isostructural. EuP and TbP are highly thermally stable approaching 450 °C and exhibit red- and green-light emissions from the characteristic 4 f-4 f transition of the Eu 3+ and Tb 3+ , respectively. Interestingly, luminescence modulation is achieved for the chemically mixed Eu/Tb phosphonate analogues, c-Eu x Tb 2 -x P (x=1.5, 1, 0.5), and physically mixed Eu/Tb phosphonate materials, p-yEuP : zTbP (y : z=3 : 1, 1 : 1, 1 : 3), with varying the excitation wavelength. Of particular note, near-white-light emission is also achieved for c-EuTbP, p-EuP : TbP, and p-EuP : 3TbP when excited at 365 nm. Therefore, these dinuclear molecular lanthanide phosphonates emitting excitation wavelength and Eu 3+  : Tb 3+ ratio dependent luminescence might be potential candidates for color-tunable luminescence materials and white-light-emitting materials. On the other hand, the bright green-light emission makes TbP to be an excellent reusable luminescence sensor for selective detection of Fe 3+ with Stern-Volmer quenching constant (K SV ) of 9.66×10 3  M -1 and detection limit (DL) of 0.42 μM through absorption competition caused luminescence quenching effect.
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