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The magnetoelectric material has attracted multidisciplinary interest in the past decade for its potential to accommodate various functions. Especially, the external electric field can drive the quantum behaviors of such materials via the spin-electric coupling effect, with the advantages of high spatial resolution and low energy cost. In this work, the spin-electric coupling effect of Mn2+-doped ferroelectric organic-inorganic hybrid perovskite [(CH3)3NCH2Cl]CdCl3 with a large piezoelectric effect was investigated. The electric field manipulation efficiency for the allowed transitions was determined by the pulsed electron paramagnetic resonance. The orientation-included Hamiltonian of the spin-electric coupling effect was obtained via simulating the angle-dependent electric field modulated continuous-wave electron paramagnetic resonance. The results demonstrate that the applied electric field affects not only the principal values of the zero-field splitting tensor but also its principal axis directions. This work proposes and exemplifies a route to understand the spin-electric coupling effect originating from the crystal field imposed on a spin ion being modified by the applied electric field, which may guide the rational screening and designing of hybrid perovskite ferroelectrics that satisfy the efficiency requirement of electric field manipulation of spins in quantum information applications.
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Magnetic molecules are promising candidates for quantum information processing (QIP) due to their tunable electron structures and quantum properties. A high spin Co(II) complex, CoH2dota, is studied for its potential to be used as a quantum bit (qubit) utilizing continuous wave (CW) and pulsed electron paramagnetic resonance (EPR) spectroscopy at low temperature. On the X-band microwave energy scale, the system can be treated as an effective spin 1/2 with a strongly anisotropic g-tensor resulting from the significant spin-orbital coupling. An experimental and theoretical study is conducted to investigate the anisotropic Rabi oscillations of the two magnetically equivalent spin centres with different orientations in a single crystal sample, which aims to verify the relationship between the Rabi frequency and the orientation of the g-tensor. The findings of this study show that an effective quantum manipulation method is developed for orthorhombic spin systems.
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Achievement of the intrinsic activity by in situ electrochemical reconstruction has been becoming a great challenge for designing a catalyst. Herein, an effective electrochemical strategy is proposed to reconstruct the surface of the CF-CuO/CeO2 precursor. Under the stimulation of oxidative/reductive potential, abundant active sites were successfully generated on the surface of CF-CuO/CeO2. Remarkably, the implantation of oxygen vacancy-rich CeO2 synergistically optimizes the chemical composition and electronic structure of CF-CuO/CeO2, greatly promoting the generation of active species. Systematic electrochemical experiments indicate that the superior catalytic performance of reconstructed CF-CuO/CeO2 could be attributed to CuOOH/CeO2 and Cu2O/Ce2O3 active species, respectively. The oxidative-/reductive-activated CF-CuO/CeO2 was further employed in a paired cell for the synergistic catalysis of hydroxymethylfurfural oxidation with 4-nitrophenol hydrogenation. As a result, nearly 100% Faraday efficiency for furandicarboxylic acid/4-aminophenol production was achieved in the paired system (-0.9 V vs Ag/AgCl, 1.5 h). Therefore, the electrochemical reconstruction via oxidative/reductive activation has been confirmed as a feasible approach to significantly excite the intrinsic activity of a catalyst.
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Discovering new functional genes and developing high-performance materials are the goals being pursued by scientists. In this work, we successfully obtained a second-order nonlinear optical (NLO) material via the aqueous solution method, Y[N(CN)2 ]4 [NH(C2 H5 )3 ] â 3H2 O, which is the first NLO material with the anionic group N(CN)2 - . Remarkably, this material is not only strongly NLO-active at 1064â nm with a response of about 2.8 × KH2 PO4 , but also possesses a short UV absorption edge of 250â nm. In-depth first-principles calculations illustrate well that the optical properties are mainly from the strong interaction of N, C and Y atoms. This result indicates that the N(CN)2 - anion may be a new NLO functional gene. This work enriches the diversity of NLO functional genes and materials.
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ÂnionsRESUMO
Birefringent materials play a key role in modulating the polarization of light and thus in optical communication as well as in laser techniques and science. Designing new, excellent birefringent materials remains a challenge. In this work, we designed and synthesized the first antimony(III) fluoride oxalate birefringent material, KSb2 C2 O4 F5 , by a combination of delocalized π-conjugated [C2 O4 ]2- groups, stereochemical active Sb3+ cations, and the most electronegative element, fluorine. The [C2 O4 ]2- groups are not in an optimal arrangement in the crystal structure of KSb2 C2 O4 F5 ; nonetheless, KSb2 C2 O4 F5 exhibits a large birefringence (Δn=0.170 at 546â nm) that is even better than that of the well-known commercial birefringent material α-BaB2 O4 , even though the latter features an optimal arrangement of π-conjugated [B3 O6 ]3- groups. Based on first-principles calculations, this prominent birefringence should be attributed to the alliance of planar π-conjugated [C2 O4 ]2- anions, highly distorted SbO2 F2 and SbOF3 polyhedra with a stereochemically active lone pair. The combination of lone-pair electrons and π-conjugated systems boosts the birefringence to a large extent and will help the development of high-performance birefringent materials.
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Accurately designing and synthesizing new deep-ultraviolet (deep-UV) nonlinear optical (NLO) crystals that are limited by the so-called "200 nm wall" on their transparency windows remain challenging. On the basis of a bandgap-directed computer-aided material design approach, two new NLO sulfates, KMgSO4F and KZnSO4F, are designed and successfully synthesized. They feature three-dimensional frameworks closely related to the commercial NLO crystal, KTiOPO4 (KTP). Remarkably, the transmittance spectrum based on a single crystal indicates that the transparency window of KZnSO4F is significantly blue-shifted to <190 nm from 350 nm for KTP. The microscopic origin of this significant transparent window blue shift is illustrated well by first-principles calculations. This work pushes the transparency windows of KTP-like NLO sulfates into the deep-UV spectral region for the first time and will pave a prospective way to the accurate design and synthesis of new deep-UV NLO materials.
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It remains a challenge to develop UV nonlinear optical (NLO) crystals that can achieve a desirable trade-off on UV absorption edge, second harmonic generation (SHG), and birefringence. Here we report a thiosulfate UV NLO crystal of a 2D van der Waals layered structure, [C(NH2)3]2SO3S. Remarkably, this thiosulfate realizes the desired trade-off, with a short absorption edge of 254 nm, a strong SHG response of approximately 2.8 times that of the benchmark KH2PO4, and a sufficient birefringence of 0.073 at the wavelength of 546 nm. In addition, it exhibits strong in-plane anisotropy of the SHG intensity. According to the first-principles calculations, the non-π-conjugated [SO3S]2- anion is the dominant SHG functional gene, while the π-conjugated [C(NH2)3]+ cation serves as the functional gene of birefringence. This is different from common UV NLO materials whose functionals of SHG and birefringence are the same. These findings indicate that combining different function genes may be an effective strategy to develop outstanding NLO materials with the desirable property trade-off.
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Antimony(III) borates with a stereochemical active lone pair remained unknown, although the first antimony borate was reported more than twenty years ago. Now, the first antimony(III) borate in a closed system is successfully synthesized, namely SbB3 O6 . Remarkably, SbB3 O6 not only exhibits an exceptional linear optical response, that is, birefringence of Δn=0.290 at the wavelength of 546â nm, which is the largest among borates, but also has a strong nonlinear optical response of 3.5 times larger than the benchmark KH2 PO4 , exceeding those of most borates. Theoretical calculations reveal that the coexistence of strong linear and nonlinear optical responses in SbB3 O6 should be attributable to the synergistic effect of π-conjugated B-O anionic groups and Sb3+ with stereochemically active lone pair. This work provides a new class of optical bi-functional materials with potential prospects in integrated optical devices.
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Birefringent materials, which can modulate the polarization of light, are almost exclusively limited to oxides. Peroxides have long been overlooked as birefringent materials, because they are usually not stable in air. Now, the first peroxide birefringent material Rb2 VO(O2 )2 F is reported, the single crystals of which keep transparency after being exposed in the air for two weeks. Interestingly, Rb2 VO(O2 )2 F does not feature an optimal anisotropic structure, but its birefringence (Δn=0.189 at 546â nm) exceeds those of the majority of oxides. According to the first-principles calculations, this exceptional birefringence should be attributed to the strong electronic interactions between localized π orbital of O2 2- anions and V5+ 3d orbitals, which may be also favorable to the stability in the air for Rb2 VO(O2 )2 F. These findings distinguish peroxides as a brand-new class of birefringent materials that may possess birefringence superior to the traditional oxides.
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A new pair of multifunctional Zn(II)-Dy(III) enantiomers based on the chiral Schiff-base ligands [R,R-ZnLDy(H2O)(NO3)3] (1R2R-ZnDy) and [S,S-ZnLDy(H2O)(NO3)3] (1S2S-ZnDy) (H2L = phenol, 2,2'-[[(1R,2R/1S,2S)-1,2-diphenyl-1,2-ethanediyl]bis[(E)-nitrilomethylidyne]]bis[6-methoxy]) was synthesized and characterized. Magnetic studies indicate that 1R2R-ZnDy behaves as a single-molecule magnet. Enantiomers 1R2R-ZnDy and 1S2S-ZnDy show chiroptical activity and circularly polarized luminescence in the N,N-dimethylformamide (DMF) solution. The chiral Zn(II)-Dy(III) complexes display magnetic circular dichroism signals at room temperature. Accordingly, these complexes will inspire intriguing research on single-molecule magnets with circular polarization of luminescence activity and magneto-optic effects, which will give new clues to design multifunctional molecular magnetic materials.
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High-performance bi-functional materials are in urgent demand for the next-generation integrated optical devices. In this work, we successfully synthesized the first tricyanomelaminate with bi-functional optical responses, namely Cs3C6N9â¢H2O (I), from its analogue Na3C6N9â¢3H2O by a facile ion exchange method. In contrast to Na3C6N9â¢3H2O, I realizes an optimal arrangement of π-conjugated (C6N9)3- anion groups in its crystal structure. As a result, the second-order nonlinear optical (NLO) response is greatly enhanced from nearly zero of Na3C6N9â¢3H2O to â¼9.8 × KH2PO4 of I. Furthermore, I exhibits a giant linear optical anisotropic response (i.e. birefringence) of 0.52 at the wavelength of 550 nm. Both responses are almost the largest among the inorganic compounds of π-conjugated rings, which indicates that I has great potential as a bi-functional optical crystal. Structural and theoretical analyses reveal the microscopic origin of excellent optical properties. This work would attract a lot of interest to the persistently neglected potential of tricyanomelaminates as linear optical and NLO crystals.
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Birefringent materials are vital materials to modulate the polarization of light, and play a key role in plorization devices such as linear optical devices, optical communication devices, and fiber optic sensors. It is still a challenge to design excellent birefringent materials. Herein, we report an organic-inorganic hybrid oxalate birefringent material, (CN4H7)SbC2O4F2(H2O)0.5, by introducing organic delocalized π-conjugated [CN4H7]+ and [C2O4]2- groups, and stereochemical active inorganic SbO4F2 polyhedra. (CN4H7)SbC2O4F2(H2O)0.5 exhibits a large birefringence (Δn = 0.126@546 nm) that is almost equal to that of the well-known birefringent material α-BaB2O4. Theoretical calculations reveal that the distinguished birefringence should stem from the synergistic arrangement of π-conjugated [CN4H7]+ and [C2O4]2- planar groups, and highly distorted SbO4F2 polyhedra with a stereochemically active lone pair. The synergistic effect of π-conjugated systems and the lone pair electrons greatly boosts the birefringence, which is helpful for the development of high-performance birefringent materials.
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Hg2+ ions are one of the highly poisonous heavy metal ions in the environment, so it is urgent to develop rapid and sensitive detection platforms for detecting Hg2+ ions. In this work, a novel electrochemical and photoelectrochemical dual-mode sensor (l-Cys-Cu2O) was successfully fabricated, and the sensor exhibits a satisfactory detection limit (0.2 and 0.01 nM) for the detection of Hg2+, which is far below the dangerous limit of the U.S. Environmental Protection Agency. The linear ranges of dual-mode Hg2+ detections were 0.33-3.3 and 0.17-1.33 µM, respectively. Moreover, the sensor shows desirable stability, selectivity, and reproducibility for detecting Hg2+ ions. For river water samples, the recoveries of 96.6-101.4% (electrochemical data) and 93.0-105.6% (photoelectrochemical data) were obtained, indicating that the sensor could be successfully applied in the determination of Hg2+ ions in environmental water. Therefore, the designed sensor has a potential in the trace-level detection of Hg2+ ions.