Modulating Two Pairs of Chiral DyIII Enantiomers by Distinct β-Diketone Ligands to Show Giant Differences in Single-Ion Magnet Performance and Nonlinear Optical Response

Xi-Li Li; Ailing Wang; Minghui Cui; Congli Gao; Xiaojing Yu; Bing Su; Liming Zhou; Cai-Ming Liu; Hong-Ping Xiao; Yi-Quan Zhang

doi:10.1021/acs.inorgchem.2c01031

Modulating Two Pairs of Chiral Dy^III Enantiomers by Distinct β-Diketone Ligands to Show Giant Differences in Single-Ion Magnet Performance and Nonlinear Optical Response

Inorg Chem. 2022 Jun 20;61(24):9283-9294. doi: 10.1021/acs.inorgchem.2c01031. Epub 2022 Jun 3.

Authors

Affiliations

¹ Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, Zhengzhou 450002, P.R. China.
² Beijing National Laboratory for Molecular Sciences, Institution of Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China.
³ School of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325027, P.R. China.
⁴ Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University, Nanjing 210023, P.R. China.

PMID: 35658475
DOI: 10.1021/acs.inorgchem.2c01031

Abstract

Using Dy(dbm)₃(H₂O) and Dy(btfa)₃(H₂O)₂ to react with enantiopure N-donors, (-)/(+)-4,5-pinenepyridyl-2-pyrazine (L_R/L_S), respectively, two pairs of chiral Dy^III enantiomers, Dy(dbm)₃L_R/Dy(dbm)₃L_S (R-1-Dy/S-1-Dy) and Dy(btfa)₃L_R/Dy(btfa)₃L_S (R-2-Dy/S-2-Dy) were obtained, wherein one of the benzene rings of dbm^- (dibenzoylmethanate) in R-1-Dy/S-1-Dy is displaced by the -CF₃ group of btfa^- (4,4,4-trifluoro-1-phenyl-1,3-butanedionate) in R-2-Dy/S-2-Dy. Interestingly, this substitution results not only in giant differences in their single-ion magnetic (SIM) performances but also in their completely different nonlinear optical (NLO) responses. R-1-Dy presents a large effective energy barrier (U_eff = 265.47 K) under zero applied field, being more than 4 × R-2-Dy (61.40 K). The discrepancy on their magnetic performances has been further elucidated by ab initio calculations. Meanwhile, R-1-Dy/S-1-Dy display the strongest third-harmonic generation responses (35/33 × α-SiO₂) among the known lanthanide NLO-active coordination compounds (CCs). On the contrary, R-2-Dy/S-2-Dy exhibit moderate second-harmonic generation responses (0.65/0.70 × KDP). These results not only give the first example of the CCs with both SMM/SIM behavior and a THG response but also provide an efficient strategy for achieving the function regulation and switch in multifunctional CCs.