November 2021Vol. 40, Issue 11
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Theoretical Study of Iron Porphyrin Imine Specie of P411 Enzyme: Electronic Structure and Regioselectivity of C(sp3)-H Primary AminationLI Shuang, WEN Zi-Hao and ZHANG Min-Yi*
Chin. J. Struct. Chem. 2021, 40, 1411-1422 DOI: 10.14102/j.cnki.0254-5861.2011-3191
December 15, 2021
DFT, cytochrome P411 enzyme, C–H bond activation, enzyme catalysis
ABSTRACT
The cytochrome P411 enzyme is a variant of cytochrome P450BM3 from Bacillus megaterium whose active site is an iron porphyrin imine ([Fe(Por)(NH)]-) specie. This specie has been reported to successfully promote the primary amination of benzylic and allylic C(sp3)?H bonds. We employed density functional theory to study the electronic structure of the active site of P411 enzyme and the primary amination of C?H bond reaction that it catalyzes. The calculated spin densities and orbital values indicate the existence of resonance in this specie; namely, [(por)(–OH)FeIV–N2-–H]- ? [(por)(–OH)FeIII–N?-–H]-. The amination of C(sp3)?H bonds consists of two main reaction steps: hydrogen-atom abstraction and radical recombination, and the former is demonstrated to be the rate-determining step. Furthermore, we studied the regioselectivity of the amination of primary and secondary C(sp3)?H bonds. Our calculations indicated that the secondary C(sp3)?H bonds of the substrate would be more favored for the activation by P411 enzyme. These results provide valuable information for understanding the properties and selectivity of C?H/C?N bond-activation reactions catalyzed by the P411 enzyme or other similar enzymes. -
ArticleGraphene Oxide/Fe3O4 Magnetic Nanocomposites for Efficient Recovery of Indium
WANG Ling-Hang, QIU Zhi-Hua and CHI Li-Sheng*
Chin. J. Struct. Chem. 2021, 40, 1423-1432 DOI: 10.14102/j.cnki.0254-5861.2011-3161
December 15, 2021
adsorbent, graphene oxide, Fe3O4 magnetic nanoparticles (NPs), nanocomposites, In(Ⅲ)
ABSTRACT
Adsorbent has been widely used for the recovery and enrichment of rare metals from waste water. Herein, a graphene-based adsorbent, graphene oxide/Fe3O4 (GO/Fe3O4) nanocomposite, was prepared by a facile hydrothermal method, and characterized by X-ray diffraction, Scanning Electron Microscope, X-ray Photoelectron Spectroscopy, Zeta potential and magnetization. The material has been explored for the recovery of In from simulated waste water. The test results show that the nanocomposite has a reasonable adsorption capacity on indium in a wide pH range, e.g., the adsorption percent and quantity of In(Ⅲ) from the aqueous solutions at pH = 4 and C0 = 50 mg·L?1 are 91% and 43.98 mg·L?1, respectively. In addition, the nanocomposites maintain a 75.5% cycling capacity and a 71% removal efficiency after five continuous cycles due to their novel properties of high specific surface area and superparamagnetism. The pseudo-second-order adsorption model can be used to interpret the kinetic data. High adsorption efficiency and good reusability can make the nanocomposite a promising adsorbent for recovery of In(Ⅲ). -
ArticleBridged Effects of Various Heterocyclic Linkages in Bis-1,2,4-triazoles
WU Jin-Ting*, XU Jin, LI Hong-Bo* and ZHANG Jian-Guo
Chin. J. Struct. Chem. 2021, 40, 1433-1438 DOI: 10.14102/j.cnki.0254-5861.2011-3181
December 15, 2021
density functional theory, effect of heterocyclic linkage, energetic material, detonation?performance
ABSTRACT
There are numerous studies on nitrogen-rich heterocycles explosive design and synthesis due to their good detonation activity. A series of bistriazoles with different heterocyclic linkages were designed and calculated by density functional theory (DFT) b3lyp/6-311+G* method. The structure, detonation properties and stability of the energetic compounds have been investigated. According to the results from heats of formation (HOFs), the HOF values of bistriazole with heterocycle linkage (M1～M4) are higher than those of the corresponding diamino-heterocycle bridged ones (M5～M8). By analyzing the bond dissociation energy (BDE), -NH- is not conducive to increase the stability of the derivatives. In terms of detonation performances and stability of bistriazole derivatives, the combination of furazan or tetrazole linkages with bis-triazoles may be considered as potential candidates for energetic materials. -
ArticleNi2MIITeIV2O2(PO4)2(OH)4 (MII = Ni, Zn): Synthesis, Crystal Structure, and Magnetic Properties
CHEN Jia-Ze, ZHUANG Rong-Chuan, MI Jin-Xiao and HUANG Ya-Xi*
Chin. J. Struct. Chem. 2021, 40, 1439-1448 DOI: 10.14102/j.cnki.0254-5861.2011-3194
December 15, 2021
tellurite, phosphate, crystal structure, stereo-chemically active lone pair, centrosymmetric
ABSTRACT
Two isostructural tellurite phosphates Ni2MIITeIV2O2(PO4)2(OH)4 (MII = Ni, Zn) have been synthe- sized via hydrothermal method. Both of them crystalize in monoclinic space group C2/m (No. 12). For Ni2ZnTeIV2O2(PO4)2(OH)4, a = 19.3247(10), b = 5.9697(3), c = 4.7737(2) ?, b = 103.637(5)°, V = 535.18(5) ?3, Z = 2, Mr = 727.94, S = 1.103, Dc = 4.517 g·cm?3, μ(MoKα) = 11.434 mm–1 and F(000) = 672, the final R = 0.0369 and wR = 0.1086 for 639 observed reflections with I > 2s(I). The crystal structure of Ni2MIITeIV2O2(PO4)2(OH)4 (MII = Ni, Zn) features a 3D framework composed of [Ni2O2(PO4)2]6? layers interconnected by [MTe2O2(OH)4]2+ single chains. Different magnetic susceptibility results at low temperature of the two title compounds confirm that Zn(1) completely occupies the Ni(2) position but not partially substitutes both Ni(1) and Ni(2) position atoms. Additionally, the acentric TeO3(OH)2 tetragonal pyramids are aligned in an antiparallel manner, resulting in the crystallization of centrosymmetric (C2/m) crystal structure instead of the non-centrosymmetric crystal structure. The investigation of the origin of centrosymmetric crystal structure with strong dipole moment units provides deeper understanding for future rational design for non-centrosymmetric crystal structure. -
ArticleA Stable Polyoxometalate-based Coordination Polymer for Light Driven Degradation of Organic Dye Pollutant
WANG Man, WU Xiao-Yuan, WANG Sa-Sa and LU Can-Zhong*
Chin. J. Struct. Chem. 2021, 40, 1449-1455 DOI: 10.14102/j.cnki.0254-5861.2011-3156
December 15, 2021
polyoxometalate-based coordination polymer, photocatalysis, 1,2,4-triazole
ABSTRACT
A new POM-based coordination polymer, [Cl2CuI11(trz)8][H3SiW12O40] (1), was successfully obtained under hydrothermal reaction. The compound was characterized by single-crystal X-ray diffraction, TG analyses, IR spectra and PXRD analysis. Compound 1 shows extreme stability and outstanding catalytic activity to the degradation of organic dye pollutant. -
ArticleA New Bio-metal-organic Framework: Synthesis, Crystal Structure and Selectively Sensing of Fe(III) Ion in Aqueous MediumYIN Yu-Jie, FANG Wang-Jian, LIU Shu-Qin*, CHEN Jun, ZHANG Jian-Jun* and NI Ai-Yun
Chin. J. Struct. Chem. 2021, 40, 1456-1460 DOI: 10.14102/j.cnki.0254-5861.2011-3180
December 15, 2021
supramolecule, crystal structure, bio-metal-organic framework, Fe3+ ion, sensing
ABSTRACT
A new two-dimensional (2D) bio-metal-organic framework based on trinuclear cluster units, [Zn3(adeninate)2(CH3COO)4]?DMF (Zn–A), was synthesized by the self-assembly of biomolecule adenines with zinc ions. Topological analysis reveals its 44 connected layer structure. Remarkably, Zn–A bears high sensitivity and selectivity detection ability of iron ion with the limit of detection being 4.0 × 10-6 mol/L. -
ArticleA Water-stable Tetranuclear Cd(II) Bicyclic Complex Used for the Picric Acid DetectionWANG Ming, WANG Xiao-Mei, CHEN Ming-Yu, LIU Cheng, DING Ge and ZHOU Xin-Hui*
Chin. J. Struct. Chem. 2021, 40, 1461-1468 DOI: 10.14102/j.cnki.0254-5861.2011-3182
December 15, 2021
sensors, complex, picric acid, fluorescence
ABSTRACT
By solvothermal reaction of Cd(II) with organic ligand N,N?-bis(3,5-dicarboxylphenyl)-thiophene-2,5- dicarboxamide (H4L), a water-stable complex [Cd4(H2L)4(H2O)10]·2CH3OH·8H2O·4DMF (1, C102H120Cd4N12O64S4) has been successfully synthetized (DMF = N,N-dimethylformamide). 1 crystallizes in the triclinic space group of P?with a = 11.815(7), b = 16.209(9), c = 16.742(9) ?, α = 82.224(13)o, β = 76.741(13)o, γ = 70.313(12)o, V = 2932(3) ?3, Mr = 3115.93, Z = 1, F(000) = 1584, Dc = 1.765 Mg/cm3, μ = 0.901 mm?1, GOOF = 1.101, the final R = 0.0391 and wR = 0.1297 for 9007 observed reflections (I > 2s(I)). 1 is a tetranuclear Cd(II) bicyclic complex with strong ligand-based blue emission and can stably exist in aqueous solutions over the pH range of 2-11. 1 exhibits high sensitivity, selectivity and anti-interference capability for picric acid (PA) detection in aqueous solution by luminescent quenching. The value of quenching constant (Ksv) is 3.2 × 104 M-1 within the PA concentration range of 0~40 μM and the detection limit is 6.89 × 10-7 M. Lastly, we went into depth on possible mechanism of the luminescent quenching.
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ArticleComparison and Relation between Crystal Structures and Magnetic Properties of Two Manganese(II) Coordination Polymers Based on (Triazol-1-yl)iso/terephthalic Acid
YAN Juan-Zhi, ZHAO Dan and LU Li-Ping*
Chin. J. Struct. Chem. 2021, 40, 1469-1474 DOI: 10.14102/j.cnki.0254-5861.2011-3186
December 15, 2021
manganese(II) complexes, (triazol-1-yl)iso/terephthalic acid, crystal structure, Hirshfeld surface, magnetic properties
ABSTRACT
One new Mn(II) coordination polymer, [Mn(Htia)2(H2O)2]n·2nH2O (1, H2tia = 4-(1,2,4-triazol- 1-yl)isophthalic acid) has been synthesized in mixed solvents under solvothermal conditions. Further characterizations including single-crystal XRD, elemental analysis, IR spectroscopy, thermogravimetric analysis and powder XRD were performed to verify the structure.? Complex 1 displays a one-dimensional (1D) chain and is similar to a reported Mn(II) complex 2 {[Mn(Htta)2(H2O)2]·2H2O}n. It crystallizes in triclinic P
?space group, with a = 7.5557 (3), b = 7.5974
(3), c = 11.8448 (4) ?, α = 90.088(1)°, β = 95.863(1)°, γ = 113.668(1)°, V = 618.81(4) ?3, Z = 1, Mr = 591.36 g/mol, Dc = 1.587 mg/m3, μ = 0.609 mm-1, F(000)
= 303, GOOF = 1.062, the final R = 0.0359 and wR = 0.0818 for 4272 observed reflections
with I > 2σ(I). Based on two similar structures,
Hirshfeld surface analysis confirmed both structures are mainly stabilized by O···H/H···O
and C···H/H···C hydrogen bonds. Further, weak ferromagnetic behaviors
between adjacent Mn(II) ions in 1D chain are obtained.
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ArticleA Linear CeⅢ Complex Based on in-situ Generated N-hydroxy-1,8-naphthalenedicarboximideLIU Yang, CAO Xue-Li, WANG Wei, LI Guo-Ling, LI Shun and HUANG You-Gui*
Chin. J. Struct. Chem. 2021, 40, 1475-1481 DOI: 10.14102/j.cnki.0254-5861.2011-3190
December 15, 2021
N-hydroxy-1,8-naphthalenedicarboximide, acenaphthoquinone dioxime, rare earth, fluorescence complex, X-ray crystallography
ABSTRACT
A CeIII linear complex of N-hydroxy-1,8-naphthalenedicarboximide (HL) has been synthesized with acenaphthoquinone dioxime (acndH2) under solvothermal conditions, in which L is generated by a series of in-situ reactions starting from acndH2. X-ray crystallography reveals the coordination chains of CeIII ions are assembled into a 3D supramolecular framework via π···π interactions. The title complex has been characterized by IR and UV-Vis spectra and thermogravimetric analysis (TGA). Furthermore, the fluorescent properties study demonstrated a ligand-based emission of the CeIII complex with ~6 nm blue-shift compared with the emisision of the HL ligand. -
ArticleSynthesis, Crystal Structure and Quantum Chemistry of a Pb(II) Coordination Polymer Based on Adipic Acid and Phenanthroline DerivativesPAN Ya-Ru, LI Xiu-Mei*, LIU Bob* and ZHOU Shi
Chin. J. Struct. Chem. 2021, 40, 1482-1488 DOI: 10.14102/j.cnki.0254-5861.2011-3195
December 15, 2021
coordination polymer, hydrothermal synthesis, crystal structure, luminescence property, quantum-chemical
ABSTRACT
A new Pb(II) coordination polymer, [Pb(adip)(L)2]n (1, H2adip = adipic acid, L = 2-(4-N,N?- dimethylphenyl)- 1-H-imidazo[4,5-f][1,10] phenanthroline), was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, FT-IR, thermogravimetric, fluorescence spectrum and elemental analysis techniques. Complex 1 crystallizes in triclinic system, space group P
?with a =
11.406(3), b = 12.036(4), c = 17.520(5) ?, V = 2228.3(11)
?3, Mr = 1028.09, Dc = 1.532 g·cm-3, F(000) = 1024, μ(MoKα)
= 3.842, Rint = 0.0274 and Z = 2. The final R = 0.1055 and wR = 0.3277 for 6954 observed
reflections with I > 2σ(I). It features a one-dimensional chain linked by adip2- ligand. Moreover, complex 1 exhibits
strong green luminescence with emission peak of 514 nm. In addition, the quantum-chemical
calculations were accomplished on ?molecular fragments? extracted from the
crystal structure of 1 using the PBE0/LANL2DZ method built in Gaussian 16
Program. The calculation values denoted the
distinct covalent interaction between the coordinated atoms and Pb(II) ion.
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ArticleA Tetranuclear Cuprous Halide Cluster Exhibiting Efficient Blue Thermally Activated Delayed Fluorescence
WANG Pei, HUANG Chun-Hua, CHEN Xu-Lin and LU Can-Zhong*
Chin. J. Struct. Chem. 2021, 40, 1489-1495 DOI: 10.14102/j.cnki.0254-5861.2011-3197
December 15, 2021
cuprous complex, thermally activated delayed fluorescence, blue emission, photoluminescence
ABSTRACT
A new tetranuclear cuprous halide complex, (CuBr)4(PN)2 (PN = 2-(diphenylphosphaneyl)- 6-methoxypyridine), was synthesized and fully characterized. In solid state, this complex exhibits efficient blue emission with a photoluminescence quantum yield of 43.3% and a decay time of 19 μs at room temperature. The theoretical calculations, combined with the temperature dependence of spectroscopic properties and emission decay behaviors, indicate that the emission in the solid state originates from the 1, 3(MLCT + XLCT) excited states, which are in thermal equilibrium with a small energy gap of about 0.1 eV. -
ArticleUltrafast Nonlinear Optical Response of Two-dimensional MoS2/Bi2Te3 Heterostructure
DONG Jun-Hao, PAN Jia, YE Chen-Yub WANG Ru, HUANG Yong-Feng, ZHENG Jing-Ying, ZHAN Hong-Bing* and WANG Qian-Ting*
Chin. J. Struct. Chem. 2021, 40, 1496-1504 DOI: 10.14102/j.cnki.0254-5861.2011-3183
December 15, 2021
two-dimensional materials, nonlinear optics, ultrafast response
ABSTRACT
Controlled stacking of different two-dimensional (2D) atomic layers hold great promise for significantly optimizing the optical properties of 2D materials and broadening their applications. Here, vertical 2D MoS2/Bi2Te3 heterostructures with high crystallinity and optical quality have been successfully constructed, through drop-casting 2D Bi2Te3 flakes on chemical vapor deposition (CVD)-grown MoS2 flakes. Based on our homebuilt micro Z-scan and pump-probe measurement, we precisely investigated and compared the nonlinear optical (NLO) performance of an individual micro-sized MoS2 flake before and after stacking 2D Bi2Te3 nanoplates. Moreover, layer-dependent ultrafast carrier dynamics of CVD-grown MoS2 flakes were also explored. Owing to the efficient charge transfer from the monolayer (1 L) MoS2 to 2D Bi2Te3, the 1L MoS2/Bi2Te3 heterostructure demonstrated excellent NLO performance with superior nonlinear saturable absorption coefficient and ultrashort carrier lifetime. Our work greatly enriches our understanding of 2D heterostructure and paves the way for designing new type of tunable 2D photonics materials by combining the optical advantages of different 2D materials. -
ArticleTransparent Co3FeOx Film Passivated BiVO4 Photoanode for Efficient Photoelectrochemical Water SplittingFANG Ming, QIN Qi, CAI Qian and LIU Wei*
Chin. J. Struct. Chem. 2021, 40, 1505-1512 DOI: 10.14102/j.cnki.0254-5861.2011-3162
December 15, 2021
photoelectrochemical water splitting, bismuth vanadate, co-catalyst, cobalt-iron oxide
ABSTRACT
Photoelectrochemistry that use semiconductors to absorb sunlight for water splitting provides an effective method for the development of renewable hydrogen energy in the future. In this paper, a transparent and highly-efficient cobalt-iron oxide (Co3FeOx) nano-film was fabricated through hydrothermal method by directional adjustment of atomic ratio to promote the kinetics of BiVO4 (BVO) photoanode water oxidation. As a result, the Co3FeOx-modified BVO photoanode (Co3FeOx/BVO) exhibits an impressive photocurrent density of 4.0 mA·cm-2 at 1.23 V versus reversible hydrogen electrode (RHE), approximately 2.17-fold higher than that of bare BVO, as well as a cathodically shifted onset potential of 320 mV. Transparent catalyst nanolayer structure is clarified by ultraviolet-visible spectroscopy. In addition, the Co3FeOx/BVO photoanode has better stability, and there is no obvious activity degradation after 10 hours of reaction. This strategy provides a broad prospect for the use of water oxidation co-catalyst to achieve effective water splitting. -
ArticleIn-situ Growth of Carbon Nanosheets Intercalated with TiO2?for Improving Electrochemical Performance and Stability of Lithium-ion Batteries
HU Yan-Jie, YIN Yan-Hong*, ZHANG Ming, WU Zi-Ping* and SHEN Zhong-Rong*
Chin. J. Struct. Chem. 2021, 40, 1513-1524 DOI: 10.14102/j.cnki.0254-5861.2011-3189
December 15, 2021
carbon nanosheets, TiO2, in situ growth, template, storage lithium
ABSTRACT
In situ growth of carbon nanomaterials on active substance is a very favorable strategy for the preparation of electrode in lithium-ion batteries with excellent electrochemical performance and high stability. Small-sized TiO2 nanoparticles intercalated into carbon nanosheets (CNS@TiO2SNP-600) were successfully synthesized via in-situ polymerization-carbonization method, utilizing layered H2Ti4O9 (HTO) as template and benzidine as carbon source. The morphology and size of TiO2 are greatly influenced by carbonization temperature. The coin cell with the CNS@TiO2SNP-600 electrode demonstrates a discharge specific capacity of 430.4 mAh×g-1 at a current density of 0.1 A×g-1, and the capacity retention rate is 88.1% after 100 cycles; and it also displays a high discharge specific capacity of 101.8 mAh×g-1 at a high current density of 12.8 A×g-1. The excellent electrochemical performances can be ascribed to the capacitance effect originated from the intercalated structure of in-situ grown CNS and TiO2 nanoparticles. We believe this type of materials can be widely used in the lithium-ion batteries and other related green chemical fields. -
ArticleConstructing Versatile Hydrophilic Surfaces via in-situ AminolysisCHEN Shuo, HUANG Wei, YANG Kea XU Yan-Lian*, WANG Dong-Hui* and HUANG Wei-Guo
Chin. J. Struct. Chem. 2021, 40, 1525-1534 DOI: 10.14102/j.cnki.0254-5861.2011-3196
December 15, 2021
surface hydrophilization, in-situ aminolysis, antifogging, self-cleaning, antifouling, regeneration
ABSTRACT
Surface hydrophilization is required for numbers of applications such as biosensor, biomedical implants and marine coating. However, the preparation of hydrophilic surface from a solid substrate still suffers from limited thicknesses, complex procedures, restricted substrates and harsh conditions. Herein, a method based on in-situ aminolysis of poly(pentafluorophenyl acrylate) (pPFPA) capable of generating arbitrary hydrophilic surface is proposed, enabling high design freedom and abundant choices of hydrophilic molecules. Simply immersing pPFPA coated substrates into 3-((3-aminopropyl)dimethylammonio)propane-1-sulfonate (ADPS), β-alanine and amine-terminal poly(ethylene glycol) (NH2-PEG) solutions for two hours drastically reduces the water contact angle of the corresponding surfaces, indicating the high efficiency and excellent generality of such method. Systematical studies reveal that these coatings are able to mitigate fog formation, self-clean the oil contaminant and exhibit excellent antifouling performance against algae. Notably, relying on the fast and quantitative feature of the aminolysis, these hydrophilic surfaces possess excellent regeneration capability and well-recover their hydrophilic feature after being physically damaged. This work represents a facile and universal way to fabricate versatile hydrophilic surfaces for multi-functional applications such as self-cleaning, patterning, sensing, antifogging and anti-biofouling. -
ArticleInorganic-organic Hybrid Cathodes for Fast-charging and Long-cycling Zinc-ion BatteriesQIU Zi-Wei, FU Yu-Ru, CHEN Ming, ZHAO Jun-Mei and SUN Chuan-Fu*
Chin. J. Struct. Chem. 2021, 40, 1535-1540 DOI: 10.14102/j.cnki.0254-5861.2011-3201
December 15, 2021
zinc-ion batteries, inorganic-organic hybrid, fast-charging, cathode
ABSTRACT
Here we report the utilization of inorganic-organic?hybrid (IOH) as a new type of cathode material for aqueous Zn-ion batteries. The IOH possessing a unique lattice-water-rich layered structure achieves high long-term cycling stability (81.5% capacity retention over 1500 cycles) and ultrafast charging capability (～90% state of charge about 1 minute).
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ArticlePendant Group Effect of Polymeric Dielectrics on the Performance of Organic Thin Film TransistorsHUANG Chong-Yu, FENG Shi-Yu and HUANG Wei-Guo*
Chin. J. Struct. Chem. 2021, 40, 1541-1549 DOI: 10.14102/j.cnki.0254-5861.2011-3167
December 15, 2021
polymer dielectric, organic thin film transistor, hydrogen bonding, π-electron delocalization, noncovalent interaction
ABSTRACT
Polymer dielectric is superior to its inorganic counterparts due to not only the low cost and intrinsic flexibility, but also the readily tunable dielectric constant, surface charge trap density, charge ejection and releasing ability and dipole moment, and all these properties play decisive roles in regulating the characteristic and performances of organic thin film transistors (OTFT). However, systematical studies on the relationship between structure and properties of polymeric dielectrics are rare. To this end, a series of polymeric dielectrics with well-defined linkages (ester or amide bonds) and predesigned pendant groups (alkyl- and aromatic-groups) are synthesized in high yields. Detailed studies show that the polyamide dielectrics exhibit higher dielectric constant, surface charge trapping density, and better charge storage capability than corresponding polyester dielectrics. Further, increasing the π electron delocalization of the pendant groups generally benefits the charge storage property and transistor memory behavior. Theoretical calculation reveals that the hydrogen bonding between the linkage groups and the energy alignment between polymeric dielectric and semiconductor are responsible for the observed performance differences of OTFT with different polymeric dielectrics. These results may shine light on the design of polymeric dielectrics for OTFTs with different applications.
- Address: Fuzhou High & New Technology Industrial Zone, Shangjie, Minhou, Fuzhou, Fujian 350108, China
- Tel: (86)-591-63173769, 63173770
- E-mail: cjsc@fjirsm.ac.cn