Multifunctional Lanthanide Molecular Ferroelectrics [ <i>R</i> / <i>S</i> -H <sub>2</sub> MPPA][Ln(btfa) <sub>4</sub> ] <sub>2</sub> Constructed by Hydrogen Bond Linking Functional Blocks
Chiral molecular ferroelectrics with optical and magnetic functions have attracted widespread attention, but their rational construction is extremely challenging due to the strict requirements of crystal symmetry. Herein, based on the construction strategy of hydrogen bond linking functional blocks, two pairs of enantiomeric multifunctional lanthanide molecular ferroelectrics [<i>R</i>/<i>S</i>-H<sub>2</sub>MPPA][Ln(btfa)<sub>4</sub>]<sub>2</sub> (<b>Tb-</b><i><b>R</b></i> <b>(1)</b>, <b>Tb-</b><i><b>S</b></i> <b>(2)</b>, <b>Dy-</b><i><b>R</b></i> <b>(3)</b>, and <b>Dy-</b><i><b>S</b></i> <b>(4)</b>) were obtained by using anionic functional blocks [Ln(btfa)<sub>4</sub>]<sup>-</sup> (Ln = Tb<sup>III</sup> and Dy<sup>III</sup>, Hbtfa = 4,4,4-trifluoro-1-phenylbutane-1,3-dione) and chiral protonated amines cation [<i>R/S</i>-H<sub>2</sub>MPPA]<sup>2+</sup> (<i>R/S</i>-MPPA = (<i>R/S</i>)-2-methylpiperazine). Ferroelectric characterization and second-harmonic generation (SHG) measurements confirmed that <b>Tb-</b><i><b>R</b></i> <b>(1)</b> and <b>Dy-</b><i><b>R</b></i> <b>(3)</b> exhibit both ferroelectricity and second-order nonlinear optical (NLO) activity. At room temperature, the spontaneous polarizations (<i>P</i><sub>s</sub>) of <b>Tb-</b><i><b>R</b></i> <b>(1)</b> and <b>Dy-</b><i><b>R</b></i> <b>(3)</b> are 1.02 μC·cm<sup>-2</sup> and 1.01 μC·cm<sup>-2</sup>, respectively. Differential scanning calorimetry (DSC) revealed that the <i>P</i>2<sub>1</sub> ferroelectric phase of <b>Tb-</b><i><b>R</b></i> <b>(1)</b> and <b>Dy-</b><i><b>R</b></i> <b>(3)</b> remained stable up to 414.9 and 421.6 K. Furthermore, <b>Tb-</b><i><b>R</b></i> <b>(1)</b> exhibits obvious characteristic yellow-green luminescence of Tb<sup>III</sup> ions. <b>Dy-</b><i><b>R</b></i> <b>(3)</b> shows field-induced single-ion magnet (SIM) behavior. This study demonstrates that integrating chiral protonated amines with [Ln(btfa)<sub>4</sub>]<sup>-</sup> functional blocks can be an effective strategy for precisely constructing molecular ferroelectrics coupled to magnetic or photoluminescent properties.
Authors
- Fu-Pei Liang
- Dongcheng Liu (ORCID: https://orcid.org/0000-0002-6420-5473)
- Chun-Pu Chen
- Xiaolu Guo (ORCID: https://orcid.org/0000-0001-5380-0341)
- Ping Lu
- Ya Gao
Institutions
- Guangxi Normal University (CN)
- Guilin University of Technology (CN)
- Ministry of Education (KR)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2026-02-24
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c04895
- Primary Topic
- Silicone and Siloxane Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00