Citation: Xiufang MA, Pengfei MI, Songsong BAO, Limin ZHENG. Effect of doping on the photodimerization reaction and the modulation of magneto-optical properties of erbium- and neodymium-anthracene complexes[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(1): 270-280. doi: 10.11862/CJIC.20230409 shu

Effect of doping on the photodimerization reaction and the modulation of magneto-optical properties of erbium- and neodymium-anthracene complexes

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Centre of Advanced Microstructures, Nanjing University, Nanjing 210023, China

Corresponding author: Limin ZHENG, lmzheng@nju.edu.cn
Received Date: 27 October 2023
Revised Date: 6 December 2023

Figures(6)

Combining photoreactive anthracene moieties with lanthanide ions, we obtained three new isostructural mononuclear compounds with the formulas Ln(SCN)₂(NO₃)(depma)₂(4-hpy)₂ (Ln=Er (1Er), Nd (2Nd), Y (3Y), where depma is 9-diethylphosphonomethylanthracene, and their single molecule magnet and photodimerization behaviors were studied. All contain face-to-face π-π interacted anthracene groups that meet the Schmidt rule for a [4+4] photocycloaddition reaction. 1Er and 2Nd show characteristic near-infrared (NIR) luminescence owing to the efficient energy transfer from the ligand to the lanthanide ion, while 3Y displays excimer emission in the visible region. As a result, only 3Y underwent photocycloaddition reaction under 395 nm UV light irradiation to form [Y(SCN)₂(NO₃)(depma₂)(4-hpy)₂]_n (3Y-UV). Magnetic studies revealed a field-induced slow relaxation of the magnetization at low temperatures for compounds 1Er and 2Nd, and the dominant relaxation process was the Raman process for 2Nd. After doping Er^Ⅲ or Nd^Ⅲ into 3Y, we constructed the isomorphic samples Ln_0.1Y_0.9(SCN)₂(NO₃)(depma)₂(4-hpy)₂ (Ln=Er (1Er@Y), Nd (2Nd@Y)). Interestingly, the diluted samples exhibited an incomplete photocycloaddition reaction, accompanied by changes in their luminescence colors from yellow-green to blue. Furthermore, partial photocycloaddition of anthracene groups in 2Nd@Y led to a slight change in the magnetic dynamics, manifested by an increase in the n value of the Raman process from 3.8 (2Nd@Y) to 5.2 (2Nd@Y-UV) which is attributed to the change in its phonon structure.
- anthracene-based phosphonate complex,
- lanthanide single molecule magnet,
- photoluminescence,
- doping effect
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