4.8 Article

Photoresponsive Organic-Inorganic Hybrid Ferroelectric Designed at the Molecular Level

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 40, Pages 16990-16998

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c06048

Keywords

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Funding

  1. NSFC [21722107, 21821003, 21805312, 21671202]
  2. Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program [2017BT01C161]
  3. FCT/MEC [UIDB/50011/2020, UIDP/50011/2020]
  4. FEDER under the PT2020 Partnership Agreement
  5. Government of the Russian Federation (Act 211) [02.A03.21.0006]
  6. national funds (OE), through FCT (Fundacao para a Ciencia e a Tecnologia), I.P.

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Molecular ferroelectrics are becoming an important area of research due to their ability to form a variety of structures exhibiting the desired properties. However, the precise control over the assembly of molecular building blocks for the design and synthesis of photoresponsive molecular ferroelectrics remains a considerable challenge. Here, we report a new hybrid high-temperature ferroelectric, (Me2NH2)[NaFe(CN)(5)(NO)], by judiciously assembling inorganic photochromic nitroprusside anion, as the framework building block, and polar organic cation Me2NH2+, as the dipole-moment carrier, into the crystal lattice. Ferroelectricity arises through the synergetic ordering of Me2NH2+ below 408 K. Piezoresponse force microscopy witnessed the presence of 180 degrees ferroelectric domains and evidenced polarization switching by repeatedly applying an external electric field. Irradiation of the N-bound nitrosyl ligand (ground state) leads to two different conformations: isonitrosyl O-bound (metastable state I) and side-on nitrosyl conformation (metastable state II). Such photoisomerization realized in solid-state molecular ferroelectrics allows for the photoswitching between the ferroelectric ground state and the metastable state. These results pave the way for new design approaches toward developing next-generation photostimulated ferroelectric materials at the molecular level.

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