Ferroelastic materials have gained widespread attention as promising candidates for mechanical switches, shape memory, and information processing. Their phase-transition mechanisms usually originate from conventional order-disorder and/or displacive types, while those involving dynamic coordination bonds are still scarce. Herein, based on a strategic molecular design of organic cations, we report three new polar hybrid crystals with a generic formula of AA'RbBiCl6 (A = A' = Me3SO+ for 1; A = Me3SO+ and A' = Me4N+ for 2; A = A' = Me3NNH2+ for 3). Their A-site cations link to the [RbBiCl6]n2n- inorganic framework with lon topology through Rb-O/N coordination bonds, while their significantly different interactions between A'-site cations and inorganic frameworks provide distinct phase-transition behaviour. In detail, the strongly coordinative A'-site Me3SO+ cations prevent 1 from a structural phase transition, while coordinatively free A'-site Me4N+ cations trigger a conventional order-disorder ferroelastic transition at 247 K in 2, accompanied by a latent heat of 0.63 J g-1 and a usual "high â low" second-harmonic-generation (SHG) switch. Interestingly, the A'-site Me3NNH2+ cations in 3 reveal unusual dynamic coordination bonds, driving a high-temperature ferroelastic transition at 369 K with a large latent heat of 18.34 J g-1 and an unusual "low â high" SHG-switching behaviour. This work provides an effective molecular assembly strategy to establish dynamic coordination bonds in a new type of host-guest model and opens an avenue for designing advanced ferroelastic multifunctional materials.
Integrating NH4+ as a B'-site ion within a three-dimensional double hybrid perovskite resulted in a novel high-temperature ferroelastic, (Me3NOH)2(NH4)[Co(CN)6], which uniquely demonstrates a reversible triclinic-to-cubic phase transition at 369 K and offers a record-setting 24 orientation states, the highest ever reported among all ferroelastics.
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 (Tc) 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.
Switching materials in channels of nonlinear optics (NLOs) are of particular interest in NLO material science. Numerous crystalline NLO switches based on structural phase transition have emerged, but most of them reveal a single-step switch between two different second-harmonic-generation (SHG) states, and only very rare cases involve three or more SHG states. Herein, we report a new organic-inorganic hybrid salt, (Me3 NNH2 )2 [CdI4 ], which is an unprecedented case of a reversible three-step NLO switch between SHG-silent, -medium, -low, and -high states, with high contrasts of 25.5/4.3/9.2 in a temperature range of 213-303â K. By using the combined techniques of variable-temperature X-ray single-crystal structural analyses, dielectric constants, solid-state 13 C nuclear magnetic resonance spectroscopy, and Hirshfeld surface analyses, we disclose that this four-state switchable SHG behavior is highly associated with the stepwise-changed molecular dynamics of the polar organic cations. This finding demonstrates well the complexity of molecular dynamics in simple hybrid salts and their potential in designing new advanced multistep switching materials.
An unprecedented A2MIMIIIX6-type double perovskite adopting a fully hexagonal BaNiO3-type structure, (piperidinium)2[KBiCl6], undergoes a 2/mF1[combining macron] ferroelastic phase transition at 285 K with a spontaneous strain of 0.0615, arising from the order-disorder transition of organic cations together with the synchronous displacement of inorganic chains.
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° 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.
We showed a reversible bond-switching ferroelastic phase transition at near room temperature in a novel organic-inorganic hybrid, (Me3NNH2)2[Co(CN)6Na(H2O)], to afford a latent heat of 43.7 kJ kg-1 and a large entropy change of 146 J K-1 kg-1.
OBJECTIVE: To explore the clinical efficacy of silver needle lumbar and sacral spine approach in treating gluteal muscle syndrome. METHODS: Eighty-seven patients with gluteal muscle syndrome treated with silver needles in the Department of Rehabilitation Medicine of our hospital from September 2017 to September 2019 were selected. Except for symptoms of waist and hip pain and discomfort, all selected patients were examined by CT or MRI to confirm pathological imaging changes such as inflammatory exudation of the gluteal muscle. The 87 patients with gluteal muscle syndrome were divided into 2 groups according to the digital table method, and 42 patients in the lumbosacral approach group, including 19 males and 23 females, aged (50.70±12.45) years old, and disease duration of (1.63±1.27) years;45 cases in the buttock approach group, including 20 males and 25 females, aged (52.80±12.18) years old, with a course of disease of (1.78±1.22) years. The lumbosacral approach group was treated with spinal L1 to S2 bilateral articular process joints and L3 transverse process acupuncture needles, and the buttock approach group was treated with the gluteus medulla wing starting point and femoral trochanter stop. The VAS scores, soft tissue tenderness thresholds, and hip abductor muscle strength of the affected group were measured before and 4 weeks after treatment in the two groups. The clinical efficacy was also evaluated 4 weeks after treatment. RESULTS: After 4 weeks, the VAS score of the lumbosacral approach group was 1.26±0.70, and the buttock approach group was 1.18±0.74, which were significantly lower than those before treatment, but there was no statistical difference between the groups (P>0.05). The soft tissue tenderness threshold and ipsilateral hip abductor muscle strength were (5.51±0.70) kg and (10.34±2.19) kg in the lumbosacral approach group, and (4.78±1.05) kg, (9.33±1.42) kg in the buttock approach group. The results in the lumbosacral approach group was better than those in the buttock approach group(P<0.05). The clinical efficacy of the lumbosacral approach group:16 cases got an excellent result, 20 good, 5 fair and 1 poor;in the buttock approach group, 13 excellent, 17 good, 12 fair and 3 poor. The clinical efficacy between the two groups had statistical difference (P<0.05). CONCLUSION: In the treatment of gluteus medius syndrome with silver needle, lumbosacral approach and buttock approach can effectively relieve the pain. Compared with the improvement of soft tissue tenderness threshold and hip abductor muscle strength, the upper lumbosacral approach is more prominent, and the overall clinical effect is more significant.
Needles , Silver , Adult , Aged , Buttocks , Female , Humans , Male , Middle Aged , Muscle, Skeletal , Thigh
We present a new hybrid compound, namely (Me2NH2)[KFe(CN)5(NO)], possessing a unique nitroprusside-based inorganic host framework in 4-connected sra topology encapsulating organic guest cations. The flexible host-guest hydrogen bonds and synchronously deformed inorganic framework give rise to thermal-responsive switching behaviours on both thermal expansion and nonlinear optical properties during the phase transition at around room temperature.
It is challenging to endow polymorphs with both long-term stability and easy interconvertibility. We demonstrate an interesting example that two room-temperature polymorphs could be long-term stable yet easily interconvertible, at a pressure of â¼4.8 MPa and a temperature of 120 °C, by switching hydrogen bonds via collective reorientation of organic cations in chiral molecular perovskites.
A new hybrid compound (Me3NOH)2[ZnCl4] undergoes an above-room-temperature mmmF2/m ferroelastic phase transition and exhibits a large spontaneous strain of 0.129, owing to an order-disorder transition of organic cations.
We disclosed that acetamidinium perchlorate is a plastic crystal undergoing a near-room-temperature plastic transition. Thanks to drastic symmetry breaking during the plastic transition, it displays remarkable nonlinear optical switching with a high on/off contrast and a superior reversibility, as well as rapid dielectric switching between the high and low dielectric states.
The underlying phase transitions of ferroelectric mechanisms in molecular crystals are mainly limited to order-disorder and displacive types that are not involved in breaking of the chemical bonds. Here, we show that the bond-switching transition under ambient pressure is designable in molecular crystals, and demonstrate how to utilize the weaker and switchable coordination bonds in a novel molecular perovskite, [(CH3)3NOH]2[KFe(CN)6] (TMC-1), to afford a scarce multiaxial ferroelectrics with a high Curie temperature of 402 K and 24 equivalent ferroelectric directions (more than BaTiO3). The high-quality thin films of TMC-1 can be easily fabricated by a simple solution process, and to reveal perfect ferroelectric properties at both macroscopic and microscopic scales, suggesting TMC-1 as a promising candidate for applications in next-generation flexible electronics. The presented molecular assembly strategy, together with the achieved bond-switching ferroelectric mechanism, opens a new avenue for designing advanced ferroelectric materials.
Using bulky amides as the structure-directing agents (SDAs) is an alternative synthetic strategy for the exploration of crystalline large pore (≥12-membered ring) zeolitic imidazolate frameworks (ZIFs). Specifically, by using the bulky amides, dibutylformamide (DBF) and dipropylformamide (DPF) as solvent and imidazole (Im) as a ligand, two ZIFs mimicking the CAN and AlPO-5 (AFI) zeotypes with 12-membered ring (MR) pore openings were synthesized, and denoted as CAN-[Zn(Im)2] and AFI-[Zn(Im)2], respectively. These two materials are the first known examples of Zn(Im)2 polymorphs with 12-MR pores and AFI-[Zn(Im)2] has the largest pore apertures reported to date for ZIF materials. The concept that the bulky amides used were not simply acting as the solvent, but were in fact acting as SDAs or templates during the synthesis of the large pore ZIFs, was suggested by the closeness of the geometrical fit between the guest DBF and the can cages (composite building units) of the CAN-[Zn(Im)2].
Plastic crystals functioning with rotatable components offer new opportunities in areas such as modern optoelectronic materials. Here, by taking advantage of controllable rotation of the polar component within the ion-pair plastic-crystal system, we present two such crystals, namely, (Et4N)(CrO3X) (X = Cl or Br), which are unusual examples exhibiting two-staged thermosensitive dielectric responses above room temperature. The frequency-dependent response in the first stage is due to the structural phase transitions, whereas that in the second stage is induced by dynamic rotation of the polar halochromate anions in their NaCl-type plastic-crystal phases. The intrinsic mechanisms were also explicated by molecular dynamics simulations, providing a direct insight into the dynamic characteristics of these two compounds. These studies show that ionic plastic crystals functioning with polar groups are an attractive candidate as sensitive thermoresponsive dielectric materials.
The changeable molecular dynamics of flexible polar cations in the variable confined space between inorganic chains brings about a new type of two-step nonlinear optical (NLO) switch with genuine "off-on-off" second harmonic generation (SHG) conversion between one NLO-active state and two NLO-inactive states.
The synthesis and characterization of copolymers from styrene and 1,3-pentadiene (two isomers) are reported. Styrene/1,3-pentadiene (1:1) copolymerization with carbanion initiator yield living, well-defined, alternating (r1 = 0.037, r2 = 0.056), and highly stereoregular copolymers with 90%-100% trans-1,4 units, designed Mn s and low ÐM s (1.07-1.17). The first-order kinetic resolution and NMR spectra demonstrate that the copolymers obtained possess strictly alternating structure containing both 1,4- and 4,1-enchaiments. Also a series of copolymers with varying degrees of alternation are synthesized from para-alkyl substituted styrene derivatives and 1,3-pentadiene. The degree of alternation is strongly dependent on the polarity of solvent, reaction temperature, type of trans-cis isomer of 1,3-pentadiene and para-substituted group in styrene. The macro zwitterion forms (SPC) through the distribution of electronic charges from the donor (1,3-pentadiene) to the acceptor (styrenes) are proposed to interpret the carbanion alternating copolymerization mechanism. Owing to the versatility of the carbanion-initiating reaction, the present alternating strategy based on 1,3-pentadiene (especially cis isomer) can serve as a powerful tool for precise control of polymer chain microstructure, architecture, and functionalities in one-pot polymerization.
Alkadienes/chemistry , Pentanes/chemistry , Polystyrenes/chemistry , Polystyrenes/chemical synthesis
A family of cyano-bridged perovskite-like coordination polymers (CPs), [(CH3)nNH(4-n)]2[KFe(CN)6] (n = 1 (1), 2 (2), 3 (3), and 4 (4)), were synthesized and characterized. The differential scanning calorimetry measurements and variable-temperature single-crystal X-ray structural analyses revealed that, owing to the deformation of the host framework as well as the dynamic transition of the guest cation between the static/ordered and dynamic/disordered states, the four CPs undergo structural phase transitions (at 429, 226, 316, and 350 K, respectively) with the symmetry breakings dependent on the symmetries of the encapsulated guest cations. The modulated differential scanning calorimetry measurement suggested that the phase transitions of 1 and 3 have more striking kinetic processes related to their drastic deformation of the host framework as well as a very significant alteration of the host-guest interaction during the phase transition. Moreover, accompanying the transitions between low- and high-temperature phases, the step-like transitions between low and high dielectric states were observed in 1-3, and the corresponding change in amplitude of the dielectric constant is dependent on the total dipole moment of each cage in the high-temperature phase. The investigation on these host-guest CPs deepens the understanding of the relationship between the dipole moment of guest cations and the dielectric behaviour of materials, shedding light on the search for new switchable molecular dielectrics.
A structural phase transition induced by ligand motion was found in a new polar coordination polymer: [Cu(NCS)2(4-APy)2]n (4-APy = 4-aminopyridine). Restraining such motion in an isomorphic compound [Cu(NCS)2(4-MeAPy)2]n (4-MeAPy = 4-methylaminopyridine) results in distinct phase transition behaviour. These findings provide a new clue for modulating phase transition behaviour in known materials.
The effects of the fermentation conditions on both the biomass yield and the organic selenium yield of Thelephora ganbajun zang were studied. The components most suitable for the submerged fermentation medium were examined using the orthogonal array method; they comprised sucrose at 30 g L(-1) , carbamide 1 g L(-1) , corn steep liquor 8 g L(-1) , MgSO4 ·7H2 O 0.3 g L(-1) , KH2 PO4 0.5 g L(-1) , and NaCl 5 g L(-1) . The optimum cultivation conditions that resulted in maximal biomass yield were obtained using the response surface methodology (RSM). The conditions were as follows: initial pH, 5.84; temperature, 26.16 °C; and rotation speed, 170 rpm. Feeding sucrose led to a higher biomass yield, with a maximum of 21.20 g L(-1) . The biomass yield and the organic Se yield of T. ganbajun could reach 10.8 g L(-1) and 3256.07 mg kg(-1) , respectively, in a culture medium supplemented with 200 mg L(-1) sodium selenite (Na2 SeO3 ), which was added to the medium at 36 h after inoculation. Application of the orthogonal array method and RSM gave rise to a significant enhancement in the biomass yield of T. ganbajun. The results of these experiments indicate that T. ganbajun is a promising microorganism for selenium enrichment.
Agaricales/growth & development , Agaricales/metabolism , Fermentation , Agriculture , Biomass , Culture Media , Selenium/metabolism
