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.

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Journal
Inorganic Chemistry
Published
2026-02-24
DOI
https://doi.org/10.1021/acs.inorgchem.5c04895
Primary Topic
Silicone and Siloxane Chemistry
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article
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article

Multifunctional Lanthanide Molecular Ferroelectrics [ R / S -H 2 MPPA][Ln(btfa) 4 ] 2 Constructed by Hydrogen Bond Linking Functional Blocks

Fu-Pei Liang, Dongcheng Liu, Chun-Pu Chen, Xiaolu Guo et al.
Inorganic Chemistry
Silicone and Siloxane Chemistry
article

Multifunctional Lanthanide Molecular Ferroelectrics [ R / S -H 2 MPPA][Ln(btfa) 4 ] 2 Constructed by Hydrogen Bond Linking Functional Blocks

Fu-Pei Liang, Dongcheng Liu, Chun-Pu Chen, Xiaolu Guo, Ping Lu, Ya Gao
article en

Abstract

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.

Inorganic ChemistryVol. 65(9)
Guangxi Normal University (CN), Guilin University of Technology (CN), Ministry of Education (KR)
Openalex Percentile: Top 47%
Silicone and Siloxane Chemistry
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