Two host–guest grown ether supramolecules show switchable phase transition, dielectric and second-harmonic generation effect

Ye, Xing; He, Wenhui; Wei, Jing; Wei, Zhenhong; You, Xiao‐Zeng; Cai, Hu

doi:10.1039/d2dt01826h

Cited by 5 publications

(3 citation statements)

References 49 publications

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“…Through our continuous exploration of multifunctional materials, we focused on designing spherical molecular structures to induce structural phase transitions. − While the crystal structure of the compound [1S,4S-2,5–2.1.1-H 2 dabch]Br 2 has been previously reported, our experimental findings suggest that this compound does not manifest characteristics such as DSC or SHG behaviors. On this basis, we explore the discovery that [1S,4S-2,5–2.2.1-H 2 dabch]I 2 serves as a promising phase-transition and second harmonic generation (SHG) material.…”

Section: Introductionmentioning

confidence: 94%

Alkali Metal Organic–Inorganic Hybrid Compounds with Different Crystal Dimensions Show Phase-Transition, Dielectric, and SHG Properties Based on a Quasi-Spherical Amine (1S,4S)-2,5-Diazabicyclo[2.2.1]heptane

Guo,

Yang,

et al. 2023

Inorg. Chem.

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Reactions of a chiral and quasi-spherical molecule [1S,4S-2,5−2.2.1-H 2 dabch]I 2 (1) with alkali metal halide MX (M = Na, K, Cs; X = Cl, Br) at room temperature produced a series of organic−inorganic hybrid (OIH) materials 4). The single-crystal X-ray diffraction analysis revealed that the organic−inorganic framework structures comprised of the templating ligand and alkali metal halides (NaBr, CsCl, KBr) displayed dimensions spanning from one-dimensional (1D) to three-dimensional (3D). Moreover, the results of both differential scanning calorimetry (DSC) and dielectric measurements demonstrated that compounds 1−4 displayed reversible, high-temperature phase transitions and noticeable dielectric anomalies. In addition, the temperature-dependent second harmonic generation (SHG) results revealed crystals 1 and 3 can switch from the SHG-ON to the SHG-OFF state, which was proved by the variable-temperature X-ray diffraction. This research aims to streamline the exploration of multifunctional second harmonic generation (SHG) and dielectric materials that have been synthesized using chiral ligands and alkali metals. This will provide researchers with enhanced opportunities to delve further into this specific research domain.

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Section: Introductionmentioning

confidence: 94%

Alkali Metal Organic–Inorganic Hybrid Compounds with Different Crystal Dimensions Show Phase-Transition, Dielectric, and SHG Properties Based on a Quasi-Spherical Amine (1S,4S)-2,5-Diazabicyclo[2.2.1]heptane

Guo,

Yang,

et al. 2023

Inorg. Chem.

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“…Switching material is a kind of material whose internal crystal structure produces on or off states stably and reversibly without changing chemical composition under external stimulation (such as temperature, pressure, and electricity). − Making use of the characteristics of these two states, it is still a hot research field to apply them in electronic storage, data communication, sensors, and other fields. ,− At present, there are many studies on switching materials with reversible phase change and dielectrics, but it is still difficult to design and synthesize switching materials with the SHG effect. This is because only the crystals crystallized in the noncentrosymmetric space group will have the reversible SHG signal.…”

Section: Introductionmentioning

confidence: 99%

Three-Dimensional Perovskite Phase Transition Materials with Switchable Second Harmonic Generation Properties Introduced by Homochiral (1S,4S)-2,5-Diazabicyclo[2.2.1]-heptane

Rao

You

et al. 2023

Inorg. Chem.

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Switchable second harmonic generation (SHG) materials have potential applications in information storage, signal processing, and so on because they can switch between SHG-on and SHG-off states. In this work, we designed and synthesized three organic−inorganic hybrid Rb halide three-dimensionalThe selection of homochiral organic cations ensures that the compounds 1∼3 crystallize in the noncentrosymmetric and chiral space group P2 1 2 1 2 1 , which further leads to reversible SHG responses of the three compounds. Through differential scanning calorimetry (DSC) and dielectric measurements, it revealed that the phase transition point of the compounds 1∼3 increased with RbCl, RbBr, and RbI. This is because the hydrogen interaction H•••X between the inorganic framework [RbX 3 ] n and the organic cation [1S,4S-2,5-2.2.1-H 2 dabch] 2+ is increased with the order of I > Br > Cl. This study can provide an effective molecular design strategy for the exploration and construction of temperature-tunable SHG switching materials.

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“…The six highly electronegative O atoms in 18-crown-6 (host) act as effective hydrogen-bond acceptors for the substituted ammonium ions (guest). A variety of guests like 4-methoxyanilinium (4-MOA) [ T c = 153 K], 2,6-diisopropylanilinium (DIPA) [ T c = 132 K], protonated 4-aminotetrahydrothiopyran (ATHTP) [ T c = 392 K], protonated 3-cyclopentene amine (Hcta) [ T c = 403 and 394 K for anion = BF 4 – and ClO 4 – respectively], and 2,6-difluorobenzylamine (DFBA) [ T c = 377 K (X = ClO 4 – ) and 391 K (X = ReO – )] have been designed. Solvents like acetonitrile have also been shown to control the phase transition for guest (cation)F 2 CHCH 2 NH 3 + .…”

Section: Introductionmentioning

confidence: 99%

Role of Momentum Matching in Increasing the Curie Temperature for Ferroelectricity in Host–Guest Complexes

Mandal,

Mukhopadhyay,

Datta

2023

J. Phys. Chem. C

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Multicomponent organic crystals having rotational flexibility can serve as excellent templates for molecular ferroelectricity. Inducing rigidity within the solid can arrest the ease for rotational transition from the ferroelectric to the paraelectric phase. By replacing the small and floppy BF 4 − anion by the bulky TFSA (bis(trifluoromethanesulfonyl)ammonium) anion, Xiong and co-workers could achieve an unparalleled T c = 415 K in the host−guest system: [(MeO−C 6 H 4 −NH 3 + )(18-crown-6)(TFSA)]. In this work via density functional theory (DFT) and classical MD simulations, we reveal that the heavy and structurally rigid TFSA anion provides a significant rotational barrier for the paraelectric relaxation from the uniaxial configuration. Among the two anions, the axle-like rotation and the bola-like rotation of the cation (MeO−C 6 H 4 −NH 3 + ) give the maximum relative barrier for the TFSA anion. While the [(MeO−C 6 H 4 −NH 3 + )(18-crown-6)(BF 4 )] crystal shows structural disorders well below 300 K, the presence of the TFSA anion ossifies it significantly at room temperature. This is also in agreement with the completely disordered intermolecular dipolar orientations for anion = BF 4 − while dipoles are highly oriented for the TFSA anion at room temperature. Momentum matching between the rotational component and the anion is found to be an excellent strategy to increase T c for ferroelectricity in these classes of systems.

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Two host–guest grown ether supramolecules show switchable phase transition, dielectric and second-harmonic generation effect

Abstract: The excellent properties of host-guest crown ether inclusions in phase transition, dielectric and second-order nonlinear optical properties have attracted much attention. In this paper, we successfully designed and prepared two...

Cited by 5 publications

References 49 publications

Alkali Metal Organic–Inorganic Hybrid Compounds with Different Crystal Dimensions Show Phase-Transition, Dielectric, and SHG Properties Based on a Quasi-Spherical Amine (1S,4S)-2,5-Diazabicyclo[2.2.1]heptane

Alkali Metal Organic–Inorganic Hybrid Compounds with Different Crystal Dimensions Show Phase-Transition, Dielectric, and SHG Properties Based on a Quasi-Spherical Amine (1S,4S)-2,5-Diazabicyclo[2.2.1]heptane

Three-Dimensional Perovskite Phase Transition Materials with Switchable Second Harmonic Generation Properties Introduced by Homochiral (1S,4S)-2,5-Diazabicyclo[2.2.1]-heptane

Role of Momentum Matching in Increasing the Curie Temperature for Ferroelectricity in Host–Guest Complexes

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