Co-reporter:Lin Zhou, Xuan Zheng, Ping-Ping Shi, Zainab Zafar, Heng-Yun Ye, Da-Wei Fu, and Qiong Ye
Inorganic Chemistry March 20, 2017 Volume 56(Issue 6) pp:3238-3238
Publication Date(Web):March 6, 2017
DOI:10.1021/acs.inorgchem.6b02508
A new perovskite-like inorganic–organic hybrid compound [Et3(n-Pr)P][Cd(dca)3] (1) (where [Et3(n-Pr)P]+ is the propyltriethylphosphonium cation and dca is a dicyanamide ligand) was discovered to undergo three reversible phase transitions at 270 K (T1), 386 K (T2), and 415 K (T3), respectively. The variable-temperature single-crystal X-ray structural analyses reveal that these sequential phase transitions originate from the deformations of the [Cd(dca)3]− frameworks and the concomitant reorientations of the [Et3(n-Pr)P]+ guest cations. It is found that 1 possesses a sensitive nonlinear optical (NLO) switching at T2 with a large contrast of ∼40 within a narrow temperature range of ∼7 K. Furthermore, 1 shows intriguing photoluminescence (PL) property, and the PL intensity suffers a plunge near T3. The multiple phase transitions, switchable NLO and tunable luminescent properties simultaneously exist in this inorganic–organic perovskite-like hybrid compound, suggesting its great potential application in molecular switches and photoelectric field.
Co-reporter:Chang Xu, Wan-Ying Zhang, Qiong Ye, and Da-Wei Fu
Inorganic Chemistry December 4, 2017 Volume 56(Issue 23) pp:14477-14477
Publication Date(Web):November 13, 2017
DOI:10.1021/acs.inorgchem.7b02055
Switchable materials, due to their potential applications in the fields of sensors, photonic devices, digital processing, etc., have been developed drastically. However, they still face great challenges in effectively inducing multiple molecular switching. Herein organic–inorganic hybrid compounds, an emerging class of hydrosoluble optoelectronic-active materials, welcome a new member with smart unique optical/electrical (fluorescence/dielectric) dual switches (switching ON/OFF), that is, [C5H13NBr][Cd3Br7] (1) in the form of both a bulk crystal and an ultraflexible monodirectional thin film, which simultaneously exhibits fast dielectric/fluorescent dual switching triggered by an optical/thermal/electric signal with a high signal-to-noise ratio of 35 (the highest one in the known optical/dielectric dual molecular switches). Additionally, the exceptional stability/fatigue resistance as well as the fantastic extensibility/compactness of thin films (more than 10000 times folding over 90°), makes 1 an ideal candidate for single-molecule intelligent wearable devices and seamlessly integrated optoelectronic multiswitchable devices. This opens up a new route toward advanced light/electric high-performance switches/memories based on organic–inorganic hybrid compounds.
Co-reporter:Qiang Guo;Wan-Ying Zhang;Da-Wei Fu
Advanced Optical Materials 2017 Volume 5(Issue 24) pp:
Publication Date(Web):2017/12/01
DOI:10.1002/adom.201700743
AbstractThree Japanese scientists are awarded the 2014 Nobel Prize in Physics for the invention of a new energy-efficient light source, the blue light-emitting diode, which has great potential in photoelectric applications. However, exploring excellent blue-light materials is still a bigger challenge than red/green ones, especially those with optical-dielectric dual channels of dielectricity and photoluminescence, which are rarely reported and gradually become the main research objects and nodi in the information industry. Herein, the first molecular blue-light switching material, (4-methoxybenzylaminum)2ZnCl4 (1) with many advantages, such as light weight, easy, and environment-friendly processing, controllability, flexibility, and so on, performs optical and dielectric dual switching simultaneously in a single-molecule integrated module. And the multifunctional switching ON/OFF channels can be manipulated in the bulk crystal or unidirectional film by applying an external thermal signal, which shows a high signal-to-noise ratio of 2:1 and a strong fatigue resistance. Besides, the dense film maintains the structural retention characteristic after more than 10 000 times of folding over 90°, which is the mark of its real genius as an ultraflexible blue-light device. This finding will promote the application of blue-light materials in optoelectronic devices and open up a new era of molecule-based blue-light switchable multifunctional materials.
Co-reporter:Fu-Juan Geng;De-Hong Wu;Lin Zhou;Ping-Ping Shi;Peng-Fei Li;Ji-Xing Gao;Xuan Zheng;Da-Wei Fu
Dalton Transactions 2017 vol. 46(Issue 29) pp:9528-9534
Publication Date(Web):2017/07/25
DOI:10.1039/C7DT01780D
A bistable optical–electrical duple switch belongs to a class of highly satisfying intelligent materials that can transform optical and electrical responses simultaneously in one device. A perovskite-type high-temperature phase transition compound with one-dimensional chain-like crystal structure, ([(CH3)3PCH2OCH3][PbBr3], 1), displays remarkable bistable photoluminescent-dielectric duple switching behaviors. The noteworthy order–disorder transition of the phosphonium cation and the motions of anions contribute to the phase transition, leading to the space group P21/c at a low temperature phase to C2/c at a high temperature phase. 1 exhibits a prominent step-like dielectric anomaly at 401.0 K and demonstrates novel optical properties with a band gap of 3.54 eV. The photoluminescence intensity suddenly declines from 398 K to 408 K, which may be attributed to the occurrence of phase transition. The electron cloud distributions of the frontier orbital in compound 1 have been calculated using a DFT program.
Co-reporter:Xuan Zheng;Ping-Ping Shi;Yang Lu;Lin Zhou;Ji-Xing Gao;Fu-Juan Geng;De-Hong Wu;Da-Wei Fu
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 9) pp:1445-1450
Publication Date(Web):2017/09/12
DOI:10.1039/C7QI00300E
A new organic–inorganic hybrid compound [(CH3)3PCH2OH][Cd(SCN)3] (1) has been synthesized, which exhibits a reversible phase transition at 248.5 K confirmed by differential scanning calorimetry. The phase transition in 1 is from a centrosymmetric space group Pmcn to a non-centrosymmetric space group P21, so that 1 exhibits a switchable second harmonic generation (SHG) effect between SHG-on and SHG-off states. This phase transition also displays switchable dielectric behaviors between high and low dielectric states accompanied by the remarkable dielectric relaxation described by the Cole–Cole equation. Variable-temperature single-crystal X-ray diffraction analyses reveal that the origin of the phase transition can be attributed to the motion or reorientation of the [(CH3)3PCH2OH]+ cations and the movement of (SCN)− ions in solid-state crystals. These superior physical properties suggest that 1 could be a potential switchable dielectric and NLO relaxor-type material, which provides a new approach to design novel multiple switch materials.
Co-reporter:Fu-Juan Geng;Lin Zhou;Ping-Ping Shi;Xiao-Li Wang;Xuan Zheng;Yi Zhang;Da-Wei Fu
Journal of Materials Chemistry C 2017 vol. 5(Issue 6) pp:1529-1536
Publication Date(Web):2017/02/09
DOI:10.1039/C6TC05105G
Three organic–inorganic hybrid analogues, ([Et3(n-Pr)P][Mn(dca)3]) 1, ([Et3(CH2CHCH2)P][Mn(dca)3]) 2, ([Et3(CH2OCH3)P][Mn(dca)3]) 3, [dca = dicyanamide, N(CN)2−], show similar three-dimensional perovskite frameworks, in which the guest phosphonium cations occupy the cavities. Compounds 1 and 3 belong to the orthorhombic noncentrosymmetric space group P212121 at room temperature, while compound 2 crystallizes in the monoclinic centrosymmetric space group P21/c. Differential scanning calorimetry (DSC) and dielectric measurements confirmed the phase transitions in compounds 1, 2 and 3, where subtle structural distinctions of guest cations affect the crystal lattices, phase transition temperatures and physical properties. Interestingly, compounds 1 and 3 are SHG active at room temperature and can be used as NLO switches tuned by guest cations and triggered by temperature.
Co-reporter:Xuan Zheng;Lin Zhou;Ping-Ping Shi;Fu-Juan Geng;Da-Wei Fu
Chemical Communications 2017 vol. 53(Issue 55) pp:7756-7759
Publication Date(Web):2017/07/06
DOI:10.1039/C7CC01771E
A new organic–inorganic perovskite-type compound [(CH3)3PCH2OH][CdBr3] exhibits a ferroelastic phase transition at 339 K. Domain structures were observed and analyzed. The origin of the phase transition can be attributed to the motion or reorientation of the [(CH3)3PCH2OH]+ cations and the displacement of Cd2+ and Br− ions in solid-state crystals.
Co-reporter:Xiao-Li Wang, Lin Zhou, Qiong Ye, Fu-Juan Geng, Heng-Yun Ye, Da-Wei Fu and Yi Zhang
RSC Advances 2016 vol. 6(Issue 78) pp:74117-74123
Publication Date(Web):26 Jul 2016
DOI:10.1039/C6RA14157A
An organic–inorganic hybrid compound 5-azonia-spiro[4,4]nonane tetrabromocadmium (1, [ASN]2[CdBr4], ASN = (CH2)4N(CH2)4), has been discovered as a new phase transition material. Differential scanning calorimetry (DSC) and dielectric measurements reveal that 1 undergoes dielectric anomalies which could be tuned in three evident dielectric states and switched by two sequential reversible phase transitions around 336 and 357 K, respectively. Detailed variable-temperature single-crystal structural analyses indicate that the distinct twisting motions of the flexible [ASN]+ ammonium cationic moieties and the relative reorientations of both the ions contribute to the structure phase transitions of 1 triggered by temperature. Particularly, 1 displays a switchable SHG response in the vicinity of 357 K, where the temperature-dependent dielectric permittivity of 1 changes abruptly from 8 to 15, with a large thermal hysteresis of 19 K. Therefore, such a distinctive dielectric performance discloses that 1 might be an interesting high-temperature switchable dielectric and nonlinear optical material. All these results open a new venue to design novel phase transition materials through selecting the flexible spiro-type ammonium salts.
Co-reporter:Fang-Fang Wang, Cheng Chen, Yi Zhang, Heng-Yun Ye, Qiong Ye and Da-Wei Fu
Journal of Materials Chemistry A 2015 vol. 3(Issue 24) pp:6350-6358
Publication Date(Web):26 May 2015
DOI:10.1039/C5TC01004G
A perovskite-like dielectric material, (C3N2H5)·[Mn(HCOO)3] (1), exhibiting remarkably high Tc (phase transition temperature) and pronounced dielectric anomaly, can be considered as a model of novel extremely high-temperature dielectric materials. The systematic characterizations, including detailed differential scanning calorimetry (DSC), variable-temperature single crystal X-ray and X-ray powder diffraction analyses, variable-temperature IR spectra as well as temperature-dependence and frequency-dependence dielectric measurements, reveal a sharp structural phase transition from tetragonal P21m at the HTP (high temperature phase) to monoclinic P21/c at the RTP (room temperature phase) and the mechanism of dielectric and thermal anomalies can be ascribed to the host–guest interaction coupled with the order–disorder transitions of the Mn(HCOO)3− cage and the [(C3N2H5)]+ guest, which is the result of a synergistic effect. Emphatically, the Tc (438 K) is the highest reported so far for a molecule-based dielectric material (the Tc is below room temperature for the most known formate series perovskite-like dielectrics), which makes 1 a promising candidate for molecule-based dramatically high-temperature dielectric materials and may open up new possibilities to make a large breakthrough in the potential practical applications in sensing, dielectric devices, energy storage, data storage and molecular or flexible multifunctional electronic devices.
Co-reporter:Qiang Li; Ping-Ping Shi; Qiong Ye; Hui-Ting Wang; De-Hong Wu; Heng-Yun Ye; Da-Wei Fu;Yi Zhang
Inorganic Chemistry 2015 Volume 54(Issue 22) pp:10642-10647
Publication Date(Web):October 29, 2015
DOI:10.1021/acs.inorgchem.5b01437
A new organic–inorganic hybrid switchable and tunable dielectric compound, [(CH3)4P]4[Mn(SCN)6] (1), exhibits three distinct dielectric states above room temperature and undergoes two reversible solid-state phase transitions, including a structural phase transition at 330 K and a ferroelastic phase transition with the Aizu notation of mmmF2/m at 352 K. The variable-temperature structural analyses disclose that the origin of the phase transitions and dielectric anomalies can be ascribed to the reorientation or motion of both the [(CH3)4P]+ cations and [Mn(SCN)6]4– anions in solid-state crystals.
Co-reporter:Ping-Ping Shi, Qiong Ye, Qiang Li, Hui-Ting Wang, Da-Wei Fu, Yi Zhang and Ren-Gen Xiong
Dalton Transactions 2015 vol. 44(Issue 17) pp:8221-8231
Publication Date(Web):24 Mar 2015
DOI:10.1039/C5DT00263J
Three analogue N-heterocyclic complexes, 1-propyl-1-methylpiperidinium perchlorate (1, [PMpip][ClO4]), 1-cyanomethyl-1-methylpiperidinium perchlorate (2, [CMpip][ClO4]), and 1-cyanomethyl-1-methylmorpholinium perchlorate (3, [CMmor][ClO4]) are identified as phase transition materials displaying switchable dielectric behaviors. Despite the common [ClO4]− anion and the closely related cations, compound 1 crystallizes in the orthorhombic space group P212121, but compounds 2 and 3 belong to the monoclinic space group P21/n with distinct cell dimensions. Compounds 1, 2 and 3 undergo reversible phase transitions around 199, 387 and 416 K, respectively, accompanied by notable step-like dielectric anomalies which could be switched by the phase transition and be tuned in distinct dielectric states. The respective dielectric constants in the high dielectric states are 1.2, 2.2 and 3.2 times that in the low dielectric states for compounds 1, 2 and 3. Generally, these differences in the phase transitions and dielectric properties are caused by the distinct molecular structures and hydrogen-bonding conformations resulting from the structural variations in the side-chain and the ring structure.
Co-reporter:Ping-Ping Shi;Hui-Ting Wang;Qiang Li;Da-Wei Fu;Yi Zhang
European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 20) pp:3255-3263
Publication Date(Web):
DOI:10.1002/ejic.201500409
Abstract
Tetramethylphosphonium dichromate ([(CH3)4P]2[Cr2O7], 1) undergoes a reversible phase transition at around 221 K. The results of the variable-temperature single-crystal X-ray structural analyses and the rotational potential energy calculations suggest that the phase transition is probably related to the order–disorder transition of the [Cr2O7]2– anion. The change of the space group from Pa-3 at room temperature to Pbca at low temperature is reflected in the peak-like dielectric response. Tetraethylphosphonium trichromate ([Et4P]2[Cr3O10], 2) crystallizes in the monoclinic space group P21/c at room temperature. Upon cooling and heating, the step-like dielectric anomalies observed at around 270 K indicate a reversible phase transition. Moreover, the rotational potential energy calculations certify the potential motion of the [Cr3O10]2– anion, being related to the phase transition. These findings open a new approach to the design of complexes that show phase transitions coupled with unusual dielectric properties.
Co-reporter:Hui-Ting Wang, Qiang Li, Ping-Ping Shi, Lin Zhou, Yi Zhang, Qiong Ye, Da-Wei Fu
Inorganic Chemistry Communications 2015 Volume 62() pp:85-90
Publication Date(Web):December 2015
DOI:10.1016/j.inoche.2015.10.031
•High temperature phase transitions•DSC and dielectric analyses of 1 and 2 confirm the phase transitions at 360.0 K and 381.0 K.•The order–disorder FeCl4− and the orientational motions of organic cations are the driving forces.The reactions of 4-(dimethylamino)pyridine (DMAP) and metal chloride in dilute hydrochloric acid yield two four-coordinate complexes, 1 (DMAP+)(FeCl4−) and 2 (DMAP+)2(CoCl42 −). The differential scanning calorimetry (DSC) measurements, temperature-dependent dielectric properties and variable-temperature single-crystal X-ray diffraction analyses of compound 1 confirmed the reversible isostructural phase transition with the same space group P21/n (No. 14) at 298 K and 373 K. The temperature-dependent single crystal structural analyses of compound 1 reveal the distinct and synchronous molecular motions of both the cationic and anionic moieties, where the orientational changes of organic cations and the order–disorder transformations of FeCl4− anions are mainly responsible for dielectric properties of compound 1. The variable-temperature structure analyses and the variable-temperature PXRD measurements reveal that compound 2 undergoes a reversible structural phase transition at around 381 K. The space groups of compound 2 change from triclinic P-1 in room temperature phase (RTP) to monoclinic C2/c in high temperature phase (HTP), accompanied by thermal and dielectric anomalies.The two four-coordinate complexes, 1 (DMAP+)(FeCl4−) and 2 (DMAP+)2(CoCl42 −), and their temperature-dependent crystal structures and dielectric properties have been synthesized and investigated. The orientational motions of organic cations and order–disorder transformations of FeCl4− anions result in the significant changes of the hydrogen bonds, however, with no change in the space group. In addition, the piezoelectric and SHG measurements were performed on compound 1 to further confirm the same centrosymmetric space group in both room and high temperature phases. Compound 2 undergoes a reversible structural phase transition at around 381.0 K. Their structural changes are reflected in the reversible dielectric transitions.DSC and dielectric analyses of 1 and 2 confirm the phase transitions at 360.0 K and 381.0 K, respectively.
Co-reporter:Ping-Ping Shi, Qiong Ye, Qiang Li, Hui-Ting Wang, Da-Wei Fu, Yi Zhang, and Ren-Gen Xiong
Chemistry of Materials 2014 Volume 26(Issue 20) pp:6042
Publication Date(Web):September 30, 2014
DOI:10.1021/cm503003f
Two inorganic–organic hybrid compounds with zero-dimensional crystal structures, tetramethylphosphonium tetrachloroferrate(III) (compound 1, [(CH3)4P][FeCl4]) and tetramethylphosphonium tetrabromoferrate(III) (compound 2, [(CH3)4P][FeBr4]), are discovered as multifunctional materials exhibiting simultaneously switchable dielectric, magnetic, and optical properties. Despite the analogue chemical formulas, compounds 1 and 2 crystallize in the different noncentrosymmetric space groups, that is, P63mc and F4̅3m, and exhibit distinct responses in the three above-mentioned physical channels, especially for the magnetic property. Compound 1 undergoes dielectric anomalies which could be tuned in three distinct dielectric states and switched by the sequential phase transitions around 362 and 436 K, respectively. The symmetry breaking occurring during the first phase transition is confirmed by the switchable temperature-dependent second harmonic generation (SHG) effect. Weak antiferromagnetic interactions are also found in compound 1 below room temperature. In contrast, the continuous phase transitions occur at 353 and 359 K in compound 2, together with the steplike dielectric anomalies which also could be tuned in three distinct dielectric states. Except for the switchable SHG effect and the antiferromagnetic interactions stronger than compound 1, compound 2 displays magnetic bistability in the vicinity of the second phase transition, with a thermal hysteresis of 6 K.
Co-reporter:Li-Hui Kong, Da-Wei Fu, Qiong Ye, Heng-Yun Ye, Yi Zhang, Ren-Gen Xiong
Chinese Chemical Letters 2014 Volume 25(Issue 6) pp:844-848
Publication Date(Web):June 2014
DOI:10.1016/j.cclet.2014.05.028
The title compound, tetramethylammonium nickel nitrite [(CH3)4N][Ni(NO2)3], has a hexagonal perovskite-type structure with formula ABX3. It undergoes two reversible phase transitions occurring at about 409.1 and 428.4 K, associated with dielectric transitions. DSC measurement and dielectric measurement confirm the transition. The variable-temperature X-ray structural determinations and the powder X-ray diffraction (PXRD) experiments reveal that this compound has the same space group P3¯m1 (No. 164) at 293 K, 413 K and 438 K. The phase transitions are caused by the rotation of the [(CH3)4N]+ cation.The most distinct difference between the room-temperature and the high-temperature structures is the rotation of tetramethylammonium, which is the driving force of the phase transitions.
Co-reporter:Qiang Li;Hui-Ting Wang
Acta Crystallographica Section C 2014 Volume 70( Issue 10) pp:992-997
Publication Date(Web):
DOI:10.1107/S2053229614020853
The one- and two-dimensional polymorphic cadmium polycarboxylate coordination polymers, catena-poly[bis[μ2-2-(2-methyl-1H-benzimidazol-1-yl)acetato-κ3N3:O,O′]cadmium(II)], [Cd(C10H9N2O2)2]n, and poly[bis[μ2-2-(2-methyl-1H-benzimidazol-1-yl)acetato-κ3N3:O,O′]cadmium(II)], also [Cd(C10H9N2O2)2]n, were prepared under solvothermal conditions. In each structure, each CdII atom is coordinated by four O atoms and two N atoms from four different ligands. In the former structure, two crystallographically independent CdII atoms are located on twofold symmetry axes and doubly bridged in a μ2-N:O,O′-mode by the ligands into correspondingly independent chains that run in the [100] and [010] directions. Chains containing crystallographically related CdII atoms are linked into sheets viaπ–π stacking interactions. Sheets containing one of the distinct types of CdII atom are stacked perpendicular to [001] and alternate with sheets containing the other type of CdII atom. The second complex is a two-dimensional homometallic CdII (4,4) net structure in which each CdII atom is singly bridged to four neighbouring CdII atoms by four ligands also acting in a μ2-N:O,O′-mode. A square-grid network results and the three-dimensional supramolecular framework is completed by π–π stacking interactions between the aromatic ring systems.
Co-reporter:Ping-Ping Shi, Su-Wen Sun, Ming-Liang Liu, Li-Hui Kong, Qiong Ye
Inorganic Chemistry Communications 2013 Volume 37() pp:84-88
Publication Date(Web):November 2013
DOI:10.1016/j.inoche.2013.09.003
•The novel salt, [(CH3)2NH2]2[Ni(mnt)2], shows a 0 dimensional cation–anion structure.•The variation of hydrogen bonds affects the temperature-dependent structure of the complex.•The structural changes are reflected in the reversible dielectric transition.The title compound bis(dimethylammonium) bis(dicyanoethene-1,2-dithiolato)-nickel (II) undergoes a reversible dielectric transition occurring at about 260 K. The variable-temperature X-ray structural determinations reveal that both phases are monoclinic, space group C2/c with a = 16.383(3), b = 9.521(5), c = 13.631(3) Å, β = 118.28(3)°, V = 1872.5(8) Å3 at the room temperature (293 K), and with a = 15.885(5), b = 9.418(0), c = 13.771(3) Å, β = 116.89(3)°, V = 1837.4(8) Å3 at the low temperature (93 K). The [Ni(mnt)2]2 − anions form a non-uniform stacking pattern and interact with the [Me2NH2]+ cations by N–H∙∙∙S, N–H∙∙∙N hydrogen bonds, for the two phases. With temperature increasing, the cations and anions are shifting and thus result in the significant changes of the hydrogen bonds. The effect of these shifts is reflected in the dielectric behavior of the [Me2NH2]2[Ni(mnt)2] salt (mnt2 − = maleonitriledithiolate).The novel complex bis(dimethylammonium) bis(dicyanoethene-1,2-dithiolato)-nickel (II), [Me2NH2]2[Ni(mnt)2], has been synthesized and investigated its temperature-dependent crystal structures and dielectric property. With temperature increasing from 93 K to 293 K, both the cations and anions are shifting in the stack and result in the significant changes of the hydrogen bonds, however, with no change in the space group. These structural changes are reflected in the reversible dielectric transition.
Co-reporter:Qiong Ye;Ping-Ping Shi;Zi-Qi Chen;Tomoyuki Akutagawa;Shin-ichiro Noro;Takayoshi Nakamura
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 23) pp:3732-3739
Publication Date(Web):
DOI:10.1002/ejic.201200099
Abstract
Reactions exchanging the cation in (nBu4N)[Ni(dmit)2] to cis-cyclohexane-1,4-diammonium (cis-CHDA) in the presence of [18]crown-6, benzo[18]crown-6 (B[18]crown-6) and dibenzo[18]crown-6 (DB[18]crown-6) yielded crystals of the monovalent [Ni(dmit)2] complex, namely (cis-CHDA)([18]crown-6)2[Ni(dmit)2]2 (1), (cis-CHDA)(B[18]crown-6)2[Ni(dmit)2]2 (2) and (cis-CHDA)(DB[18]crown-6)2[Ni(dmit)2]2 (3). The two ammonium groups (–NH3+) of the cis-CHDA dication at axial and equatorial positions interact with oxygen atoms of the corresponding upper and lower crown ethers to form sandwich-type supramolecular cationic structures. The lateral [Ni(dmit)2]− anion arrangements through S–S contacts along the short and long axis of [Ni(dmit)2] anions were realised in crystals of 1, 2, and 3 by the asymmetrical cis-CHDA dication. The temperature- and frequency-dependent anisotropic dielectric constants of a crystal of 1 were evaluated along the a, b and c axes, where the thermally activated motion of the structurally flexible cis-CHDA dication was consistent with the dielectric responses.
Co-reporter:Qiong Ye, Ming-Liang Liu, Zi-Qi Chen, Su-Wen Sun, and Ren-Gen Xiong
Organometallics 2012 Volume 31(Issue 22) pp:7862-7869
Publication Date(Web):May 31, 2012
DOI:10.1021/om300343j
Solvothermal reactions of CuX (X = Cl, Br) and the organic olefin ligand 1,3,5-tris(diallylaminomethyl)-2,4,6-trimethylbenzene (TTB) in the presence of acid offered two novel olefin–copper(I) coordination compounds with unprecedented CuX cluster structures. The C3 symmetry of TTB leads to the formation of a novel C3-symmetric CuX cluster in oligomer compound 1 (H3TTB[Cu4Cl3]) and CuX framework in the two-dimensional compound 2 (H3TTB[Cu8Br11]). However, the flexibility and kink of H3TTB induce olefin–copper(I) coordination compounds to crystallize in noncentrosymmetric space groups R3c and R3 for compounds 1 and 2, respectively. In addition to the bowl-like structure of the olefin ligand and C3-symmetric CuX cluster found in compound 1, such bowl-like moieties are connected by another kind of C3-symmetric CuX cluster to form a novel two-dimensional framework in compound 2. The electron cloud distributions and energy levels of the frontier orbitals in both compounds have been calculated by a DFT program. Nonlinear optical property measurement results show that both compounds are second-harmonic generation (SHG) active. Compounds 1 and 2 display no phase transition according to the measurement of the temperature dependence of dielectric properties in the temperature range 100–300 K. The close packing and large density from the high CuX/ligand ratio in compound 2 correspond to the higher dielectric constant.
Co-reporter:Qiong Ye, Ping-Ping Shi, Zi-Qi Chen, Tomoyuki Akutagawa, Shin-ichiro Noro, Takayoshi Nakamura
Inorganic Chemistry Communications 2012 20() pp: 219-224
Publication Date(Web):
DOI:10.1016/j.inoche.2012.03.012
Co-reporter:Xue-Qun Fu, Tian Hang, Qiong Ye, Ren-gen Xiong
Inorganic Chemistry Communications 2011 Volume 14(Issue 1) pp:281-284
Publication Date(Web):January 2011
DOI:10.1016/j.inoche.2010.11.014
One novel organic–inorganic hybrid compound, (EB-NH3+)(18-crown-6)·H2PO4−·2H3PO4·2.5H2O (1) (EB-NH3+ = 4-ethoxybenzenammonium; 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclo-octadecane), has been synthesized and characterized by powder X-ray, IR, thermogravimetric analysis and single X-ray structure analysis. In the structure of complex 1 the organic (EB-NH3+)(18-crown-6) supermolecular cation sheet and inorganic phosphate anion sheet arrange alternately. Compound 1 and its deuterium product 2 display excellent dielectric property with a huge dielectric permittivity deuterated effect (DEF) of 1649% (200 Hz, 300 K).In the novel organic-inorganic hybrid compound 1, organic supermolecular cation and inorganic phosphate anion sheet arrange alternately. The frequency-dependent and temperature-dependent dielectric constants measurement shows that compound 1 and its deuterium product 2 display excellent dielectric property with a huge dielectric permittivity deuterated effect (DEF) of 1649% (200Hz, 300K).Research highlights► We report one organic-inorganic hybrid compound in which the organic (EB-NH3+)(18-crown-6) supermolecular cation sheet and inorganic phosphate anion sheet arrange alternately. ► This compound and its deuterium product display a huge dielectric permittivity deuterated effect. ► The huge dielectric DEF is due to the great dielectric response of water molecules.
Co-reporter:Wei Wang, Li Zhang, Xiong-Bin Xu, Qiong Ye
Inorganic Chemistry Communications 2011 Volume 14(Issue 5) pp:626-631
Publication Date(Web):May 2011
DOI:10.1016/j.inoche.2011.01.033
Solvothermal treatments of (E)-1,3-diallyl-2-styryl-3 H -benzo[d]imidazol-1-ium bromide olefin ligand 1 and CuX (X═Br, 2 and X═Cl, 3) in the presence of methanol as solvent at 75 °C for 1 week offer organic–inorganic hybrid compound 2 and olefin–copper(I) compound 3. The conformation of olefin cation ligand affects the coordination of allyl group. Two allyl groups existing at different sides of benzoimidazole plane successfully coordinate to copper(I) centers to form olefin–copper(I) coordination compound 3, which shows two-dimensional structure of (4,4) network with [Cu6Cl4Br4]2− cluster nods. The dielectric measurement results show there is no dielectric anomaly observed within the temperature range of 120 K to 300 K for compound 3.Research Highlights► Solvothermal synthesis of olefin-copper(I) coordination compound. ► The conformation of organic ligand affects the formation of olefin-copper(I) coordination compound. ► Novel copper–halide cluster as node to construct 2D (4,4) net coordination polymer. ► High dielectric constant. ► Fluorescent influence.
Co-reporter:Yuan Zhang;Mengting Han, ;Rengen Xiong
Chinese Journal of Chemistry 2010 Volume 28( Issue 9) pp:1533-1537
Publication Date(Web):
DOI:10.1002/cjoc.201090261
Abstract
The molten reaction of 2-naphthol, 2-hydroxybenzaldehyde and tetrahydropyrrole at about 120°C yields 1-[(2-hydroxyphenyl)(pyrrolidin-1-yl)-methyl]naphthalen-2-ol, whose co-crystal (1) with 2-naphthol was characterized by X-ray single crystal diffraction, XRPD and IR. Compound 1 crystallizes in a noncentrosymmetric space group (Fdd2) with unit cell dimensions of a=2.9395(9) nm, b=3.468(3) nm, c=0.8013(8) nm, V=8.170(13) nm3, α=β=γ=90.0° and Z=8 [at 293(2) K]. The piezoelectric measurement result shows compound 1 is piezoelectrically active material with d33 value of ca. 6.2 pC/N. Temperature- and frequency-dependent dielectric constant of compound 1 were measured and showed no distinct dielectric anomaly, which suggest no phase transition within the measured temperature range (100–410 K).
Co-reporter:Tian Hang, Da-Wei Fu, Qiong Ye and Ren-Gen Xiong
Crystal Growth & Design 2009 Volume 9(Issue 5) pp:2026
Publication Date(Web):March 30, 2009
DOI:10.1021/cg800618v
Hydrothermal treatments of ZnCl2 and organic ligands afforded two novel noncentrosymmetric coordination compounds 1 and 2, respectively. 1 crystallizes in the chiral P212121 space group because of the introduction of a bent ligand 3-(2-(2-pyridyl)ethenyl)benzoic acid to the complex, whereas 2 crystallizes in hexagonal crystal system (R3) with a 3-fold axis and bears two octahedral chelate zinc cation and two [ZnBr4]2−. Both 1 and 2 display a strong second harmonic generation (SHG) response and moderate piezoelectric properties. Because of the assignment of a polar point group of chiral space group for compound 2 (R3), its electric hysteresis loop was recorded; we found that it may be a potential ferroelectric with spontaneous polarization of 0.02 μC/cm2.
Co-reporter:Qiong Ye, Tian Hang, Da-Wei Fu, Guang-Hai Xu and Ren-Gen Xiong
Crystal Growth & Design 2008 Volume 8(Issue 10) pp:3501-3503
Publication Date(Web):September 5, 2008
DOI:10.1021/cg8004129
Solvothermal treatment of a flexible olefin organic ligand and CuBr offers a novel olefin-copper(I) coordination compound. The induction of the flexible ligand leads the olefin-copper(I) organometallic compound to crystallize in a chiral or polar point group P41. The investigation of its ferroelectric property shows that the compound is a typical ferroelectric and its electric hysteresis loop shows a remanent polarization (Pr) of ca. 0.2 μC/cm2 and coercive field (Ec) of 800 V/cm.
Co-reporter:Yun-Zhi Tang, Guo-Xi Wang, Qiong Ye, Ren-Gen Xiong and Rong-Xin Yuan
Crystal Growth & Design 2007 Volume 7(Issue 12) pp:2382
Publication Date(Web):November 10, 2007
DOI:10.1021/cg070528g
The two in situ 2 + 3 intermolecular cycloaddition reactions between inorganic complexes bis(3-cyanopyrdine)copper(II)azide (A) offer homometallic and heterometallic 3D novel tetrazole coordination polymers, (3-C5H4N-CN4)2Cu(I)2 (1) and (3-C5H4N-CN4)Cu(I)Cd(II)Cl2 (2), respectively, in the presence of Lewis acid CuCl2 and CdCl2 in which A is used to replace the organic cyano group and NaN3 during Sharplessʼs tetrazole synthesis. Their interesting luminescent properties are reported.
Co-reporter:Fang-Fang Wang, Cheng Chen, Yi Zhang, Heng-Yun Ye, Qiong Ye and Da-Wei Fu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 24) pp:NaN6358-6358
Publication Date(Web):2015/05/26
DOI:10.1039/C5TC01004G
A perovskite-like dielectric material, (C3N2H5)·[Mn(HCOO)3] (1), exhibiting remarkably high Tc (phase transition temperature) and pronounced dielectric anomaly, can be considered as a model of novel extremely high-temperature dielectric materials. The systematic characterizations, including detailed differential scanning calorimetry (DSC), variable-temperature single crystal X-ray and X-ray powder diffraction analyses, variable-temperature IR spectra as well as temperature-dependence and frequency-dependence dielectric measurements, reveal a sharp structural phase transition from tetragonal P21m at the HTP (high temperature phase) to monoclinic P21/c at the RTP (room temperature phase) and the mechanism of dielectric and thermal anomalies can be ascribed to the host–guest interaction coupled with the order–disorder transitions of the Mn(HCOO)3− cage and the [(C3N2H5)]+ guest, which is the result of a synergistic effect. Emphatically, the Tc (438 K) is the highest reported so far for a molecule-based dielectric material (the Tc is below room temperature for the most known formate series perovskite-like dielectrics), which makes 1 a promising candidate for molecule-based dramatically high-temperature dielectric materials and may open up new possibilities to make a large breakthrough in the potential practical applications in sensing, dielectric devices, energy storage, data storage and molecular or flexible multifunctional electronic devices.
Co-reporter:Ping-Ping Shi, Qiong Ye, Qiang Li, Hui-Ting Wang, Da-Wei Fu, Yi Zhang and Ren-Gen Xiong
Dalton Transactions 2015 - vol. 44(Issue 17) pp:NaN8231-8231
Publication Date(Web):2015/03/24
DOI:10.1039/C5DT00263J
Three analogue N-heterocyclic complexes, 1-propyl-1-methylpiperidinium perchlorate (1, [PMpip][ClO4]), 1-cyanomethyl-1-methylpiperidinium perchlorate (2, [CMpip][ClO4]), and 1-cyanomethyl-1-methylmorpholinium perchlorate (3, [CMmor][ClO4]) are identified as phase transition materials displaying switchable dielectric behaviors. Despite the common [ClO4]− anion and the closely related cations, compound 1 crystallizes in the orthorhombic space group P212121, but compounds 2 and 3 belong to the monoclinic space group P21/n with distinct cell dimensions. Compounds 1, 2 and 3 undergo reversible phase transitions around 199, 387 and 416 K, respectively, accompanied by notable step-like dielectric anomalies which could be switched by the phase transition and be tuned in distinct dielectric states. The respective dielectric constants in the high dielectric states are 1.2, 2.2 and 3.2 times that in the low dielectric states for compounds 1, 2 and 3. Generally, these differences in the phase transitions and dielectric properties are caused by the distinct molecular structures and hydrogen-bonding conformations resulting from the structural variations in the side-chain and the ring structure.
Co-reporter:Fu-Juan Geng, De-Hong Wu, Lin Zhou, Ping-Ping Shi, Peng-Fei Li, Ji-Xing Gao, Xuan Zheng, Da-Wei Fu and Qiong Ye
Dalton Transactions 2017 - vol. 46(Issue 29) pp:NaN9534-9534
Publication Date(Web):2017/06/27
DOI:10.1039/C7DT01780D
A bistable optical–electrical duple switch belongs to a class of highly satisfying intelligent materials that can transform optical and electrical responses simultaneously in one device. A perovskite-type high-temperature phase transition compound with one-dimensional chain-like crystal structure, ([(CH3)3PCH2OCH3][PbBr3], 1), displays remarkable bistable photoluminescent-dielectric duple switching behaviors. The noteworthy order–disorder transition of the phosphonium cation and the motions of anions contribute to the phase transition, leading to the space group P21/c at a low temperature phase to C2/c at a high temperature phase. 1 exhibits a prominent step-like dielectric anomaly at 401.0 K and demonstrates novel optical properties with a band gap of 3.54 eV. The photoluminescence intensity suddenly declines from 398 K to 408 K, which may be attributed to the occurrence of phase transition. The electron cloud distributions of the frontier orbital in compound 1 have been calculated using a DFT program.
Co-reporter:Xuan Zheng, Lin Zhou, Ping-Ping Shi, Fu-Juan Geng, Da-Wei Fu and Qiong Ye
Chemical Communications 2017 - vol. 53(Issue 55) pp:NaN7759-7759
Publication Date(Web):2017/06/14
DOI:10.1039/C7CC01771E
A new organic–inorganic perovskite-type compound [(CH3)3PCH2OH][CdBr3] exhibits a ferroelastic phase transition at 339 K. Domain structures were observed and analyzed. The origin of the phase transition can be attributed to the motion or reorientation of the [(CH3)3PCH2OH]+ cations and the displacement of Cd2+ and Br− ions in solid-state crystals.
Co-reporter:Fu-Juan Geng, Lin Zhou, Ping-Ping Shi, Xiao-Li Wang, Xuan Zheng, Yi Zhang, Da-Wei Fu and Qiong Ye
Journal of Materials Chemistry A 2017 - vol. 5(Issue 6) pp:NaN1536-1536
Publication Date(Web):2017/01/10
DOI:10.1039/C6TC05105G
Three organic–inorganic hybrid analogues, ([Et3(n-Pr)P][Mn(dca)3]) 1, ([Et3(CH2CHCH2)P][Mn(dca)3]) 2, ([Et3(CH2OCH3)P][Mn(dca)3]) 3, [dca = dicyanamide, N(CN)2−], show similar three-dimensional perovskite frameworks, in which the guest phosphonium cations occupy the cavities. Compounds 1 and 3 belong to the orthorhombic noncentrosymmetric space group P212121 at room temperature, while compound 2 crystallizes in the monoclinic centrosymmetric space group P21/c. Differential scanning calorimetry (DSC) and dielectric measurements confirmed the phase transitions in compounds 1, 2 and 3, where subtle structural distinctions of guest cations affect the crystal lattices, phase transition temperatures and physical properties. Interestingly, compounds 1 and 3 are SHG active at room temperature and can be used as NLO switches tuned by guest cations and triggered by temperature.
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