Near-room-temperature dielectric switch and thermal expansion anomaly in a new hybrid crystal: (Me2NH2)[CsFe(CN)5(NO)]

Li, Qi-Yao; Li, Mao-Fan; Chen, Xiaoming; Gong, Yun; Liu, De‐Xuan; Xu, Weijian; Zhang, Wei‐Xiong

doi:10.1039/d2ce00754a

Cited by 6 publications

(4 citation statements)

References 39 publications

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“…Recently, [(CH 3 ) 2 NH 2 ][CsFe(CN) 5 (NO)] was reported to display dielectric switching, but no photoresponse was reported. [14] Finally, T-induced dielectric switching and NO photoswitching were reported for (CH 3 NH 3 )[NaFe(CN) 5 -(NO)].H 2 O. [15] These studies show the promise of (A)[MFe-(CN) 5 (NO)].xH 2 O materials, but with some key outstanding questions.…”

Section: Introductionmentioning

confidence: 93%

Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic‐Inorganic Crystal by In Situ X‐Ray Diffraction

Morris,

Bowen,

Coulson

et al. 2024

Angewandte Chemie

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The switching behavior of the novel hybrid material (FA)Na[Fe(CN)5(NO)].H2O (1) in response to temperature (T), light irradiation and electric field (E) is studied using in‐situ X‐ray diffraction (XRD). Crystals of 1 display piezoelectricity, pyroelectricity, second and third harmonic generation. XRD shows that the FA+ are disordered at room‐temperature, but stepwise cooling from 273‐100K induces gradual ordering, while cooling under an applied field (E = +40kVcm‐1) induces a sudden phase change at 140K. Structural‐dynamics calculations suggest the field pushes the system into a region of the structural potential‐energy surface that is otherwise inaccessible, demonstrating that application of T and E offers an effective route to manipulating the crystal chemistry of these materials. Photocrystallography also reveals photoinduced linkage isomerism, which coexists with but is not correlated to other switching behaviors. These experiments highlight a new approach to in‐situ studies of hybrid materials, providing insight into the structure‐property relationships that underpin their functionality.

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Section: Introductionmentioning

confidence: 93%

Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic‐Inorganic Crystal by In Situ X‐Ray Diffraction

Morris,

Bowen,

Coulson

et al. 2024

Angewandte Chemie

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“…Recently, several reports have demonstrated that the co-assembly of various organic cations with the nitroprusside anion [Fe(CN) 5 (NO)] 2– produces a new class of organic–inorganic hybrid materials with diverse structures and fascinating physical properties. − For instance, Yao et al reported a Pbcm to Cmcm phase transition at 207 K in (MA) 2 [Fe(CN) 5 (NO)] (MA = methylammonium) . However, the antiparallel arrangement of polar MA cations and their dynamical disordering cancel out the total unit cell dipole moment, preventing the emergence of long-range order and electric polarization (Figure , left).…”

Section: Introductionmentioning

confidence: 99%

Molecular Design of a Metal-Nitrosyl Ferroelectric with Reversible Photoisomerization

García

et al. 2023

J. Am. Chem. Soc.

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The development of photo-responsive ferroelectrics whose polarization may be remotely controlled by optical means is of fundamental importance for basic research and technological applications. Herein, we report the design and synthesis of a new metal-nitrosyl ferroelectric crystal (DMA)(PIP)[Fe(CN)5(NO)] (1) (DMA = dimethylammonium, PIP = piperidinium) with potential phototunable polarization via a dual-organic-cation molecular design strategy. Compared to the parent non-ferroelectric (MA)2[Fe(CN)5(NO)] (MA = methylammonium) material with a phase transition at 207 K, the introduction of larger dual organic cations both lowers the crystal symmetry affording robust ferroelectricity and increases the energy barrier of molecular motions, endowing 1 with a large polarization of up to 7.6 μC cm–2 and a high Curie temperature (T c) of 316 K. Infrared spectroscopy shows that the reversible photoisomerization of the nitrosyl ligand is accomplished by light irradiation. Specifically, the ground state with the N-bound nitrosyl ligand conformation can be reversibly switched to both the metastable state I (MSI) with isonitrosyl conformation and the metastable state II (MSII) with side-on nitrosyl conformation. Quantum chemistry calculations suggest that the photoisomerization significantly changes the dipole moment of the [Fe(CN)5(NO)]2– anion, thus leading to three ferroelectric states with different values of macroscopic polarization. Such optical accessibility and controllability of different ferroelectric states via photoinduced nitrosyl linkage isomerization open up a new and attractive route to optically controllable macroscopic polarization.

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“…This has allowed phase transition materials to have considerable utility in the areas of switchable devices, information storage, and actuators. − Among them, organic–inorganic hybrid perovskite materials are unique phase transition materials that are connected by inorganic frameworks and organic cations through a certain interaction force, integrating the advantages of inorganic phase transition materials and organic phase transition materials. − Inorganic metal frameworks show outstanding advantages in optical, semiconducting, and electrical properties. Organic cations have a flexible structure that can be easily modified and are susceptible to movement by temperature, which leads to phase transitions in the material. − The combination of these two makes organic–inorganic hybrid perovskite materials stand out among many phase transition materials by their environmental friendliness and structural tunability. − Exploiting these advantages, many functionally diverse hybrid organic–inorganic perovskite ferroelectrics have been investigated . Likewise, this unique structure of organic–inorganic hybrid perovskite materials also makes them show their brilliance in optoelectronic field. , …”

Section: Introductionmentioning

confidence: 99%

Lead-Free Semiconducting Organic–Inorganic Hybrid Perovskite with Mixed Organic Cations

et al. 2023

Crystal Growth & Design

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Hybrid perovskites with mixed organic cations have recently received extensive focus from researchers for their structural tunability, enhanced performance, and stability. However, because there are certain requirements for the size of different organic cations to form hybrid perovskites with mixed organic cations, reports on hybrid perovskites that can contain both phosphonium and ammonium cations have been rare. Here, we report an organic–inorganic hybrid perovskite (Me3PCH2CH2CH3)2(CH3CH2CH2NH3)Sb2Br9 (1) with [Me3PCH2CH2CH3]+ cations and [CH3CH2CH2NH3]+ cations. Compound 1 exhibits a reversible phase transition at 371.3/353.2 K. Compared with the organic–inorganic hybrid perovskites only with [Me3PCH2CH2CH3]+ cations or [CH3CH2CH2NH3]+ cations, the phase transition temperature of the organic–inorganic hybrid perovskite formed by mixing [Me3PCH2CH2CH3]+ cations and [CH3CH2CH2NH3]+ cations is significantly increased, and the thermal stability is improved. Structural analysis shows the disorder of [CH3CH2CH2NH3]+ cations and the twisting motion of [Me3PCH2CH2CH3]+ cations and the inorganic skeleton are the major reasons for the phase transition of 1 at high temperatures. Furthermore, 1 possesses semiconductor properties with an optical band gap of 2.945 eV. This discovery will shed light on exploring more excellent functional perovskite materials with mixed organic cations.

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Near-room-temperature dielectric switch and thermal expansion anomaly in a new hybrid crystal: (Me₂NH₂)[CsFe(CN)₅(NO)]

Abstract: A new hybrid crystal, (Me2NH2)[CsFe(CN)5(NO)], featuring a double-layered nitroprusside-based inorganic framework with cubic-like cages encapsulating organic cations, undergoes a near-room-temperature phase transition accompanying with dielectric switch and thermal expansion anomaly....

Cited by 6 publications

References 39 publications

Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic‐Inorganic Crystal by In Situ X‐Ray Diffraction

Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic‐Inorganic Crystal by In Situ X‐Ray Diffraction

Molecular Design of a Metal-Nitrosyl Ferroelectric with Reversible Photoisomerization

Lead-Free Semiconducting Organic–Inorganic Hybrid Perovskite with Mixed Organic Cations

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