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61.
Importing intramolecular hydrogen bond in phosphorescent transition metal complexes has been considered one of the excellent approaches to improve the electroluminescence performance of organic light-emitting diodes in real applications. However, the relationships between such H-bond structure and phosphorescent properties have not been theoretically revealed yet. In this study, two types of intramolecular hydrogen bonds are introduced into the two classes of traditional materials, that is, Pt(II) and Ir(III) complexes ( 1a and 2a ) to completely elucidate their influence on the structures and properties by comparing with the original phosphors ( 1b and 2b ) using density functional theory/time-dependent density functional theory for the first time. A comprehensive analysis of the geometric structures, molecular orbitals, and luminescence properties (including phosphorescence emission wavelengths and radiative and nonradiative decay processes) has been carried out. Our theoretical model highlights that complexes 1a and 2a embedded with H-bonds significantly promote the phosphorescence emission band blue-shifted and restrict molecular deformations compared with the corresponding 1b and 2b , which can provide helpful guidance to regulate and design several aspects of highly efficient blue phosphorescent emitters. 相似文献
62.
Kevin W. Gao Xi Jiang Zach J. Hoffman Gurmukh K. Sethi Saheli Chakraborty Irune Villaluenga Nitash P. Balsara 《Journal of polymer science. Part A, Polymer chemistry》2020,58(2):363-371
Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. This is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 363–371 相似文献
63.
Jing Zhang Shuhui Wang Jacques Lalevée Fabrice Morlet-Savary Elizabeth S.-H. Lam Bernadette Graff Jing Liu Feiyue Xing Pu Xiao 《Journal of polymer science. Part A, Polymer chemistry》2020,58(6):792-802
The photoinitiation abilities of three 1,2-diketones [i.e., acenaphthenequinone ( ANPQ ), aceanthrenequinone ( AATQ ), and 9,10-phenanthrenequinone ( PANQ )]-based photoinitiating systems [PISs, with additives such as iodonium salt, N-vinylcarbazole (NVK), tertiary amine, and phenacyl bromide (R-Br)] for cationic photopolymerization and free-radical photopolymerization under the irradiation of ultraviolet (UV; 392 nm) or blue (455 nm) light-emitting diode (LED) bulb are investigated. All 1,2-diketones studied exhibit ground state absorption that match with the emission spectra of UV (392 nm) or blue LED (455 nm) better than that of the well-known blue-light-sensitive photoinitiator camphorquinone (CQ). In particular, AATQ /iodonium salt/NVK can show high photoinitiating ability (with epoxide conversion yield >70%) under the UV light irradiation due to the effect of NVK. In addition, 1,2-diketone/iodonium salt (and optional NVK) systems are capable of initiating free-radical photopolymerization of methacrylates, with conversions of 50–58%. Furthermore, some 1,2-diketone/tertiary amine (and optional R-Br) combinations are found to demonstrate high efficiency to initiate free-radical photopolymerization, and 71% of methacrylate conversion can be achieved with PANQ /tertiary amine/R-Br PIS. Some 1,2-ketone-based PISs can even exhibit higher efficiency than the CQ-based systems. The photochemical mechanism of the radical generation from the 1,2-diketone-based PISs is investigated and found to be consistent with the related photopolymerization efficiency. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 792–802 相似文献
64.
Research on Chemical Intermediates - Defective TiO2 nanocrystals (D-TiO2) were synthesized by a simple, mild and green sol–gel hydrothermal method. The as-prepared sample possesses a high... 相似文献
65.
Dr. Jinwen Qin Linlin Hao Xin Wang Yan Jiang Dr. Xi Xie Prof. Rui Yang Prof. Minhua Cao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(49):11231-11240
The optimization of three-dimensional (3D) MXene-based electrodes with desired electrochemical performances is highly demanded. Here, a precursor-guided strategy is reported for fabricating the 3D SnS/MXene architecture with tiny SnS nanocrystals (≈5 nm in size) covalently decorated on the wrinkled Ti3C2Tx nanosheets through Ti−S bonds (denoted as SnS/Ti3C2Tx-O). The formation of Ti−S bonds between SnS and Ti3C2Tx was confirmed by extended X-ray absorption fine structure (EXAFS). Rather than bulky SnS plates decorated on Ti3C2Tx (SnS/Ti3C2Tx-H) by one-step hydrothermal sulfidation followed by post annealing, this SnS/Ti3C2Tx-O presents size-dependent structural and dynamic properties. The as-formed 3D hierarchical structure can provide short ion-diffusion pathways and electron transport distances because of the more accessible surface sites. In addition, benefiting from the tiny SnS nanocrystals that can effectively improve Na+ diffusion and suppress structural variation upon charge/discharge processes, the as-obtained SnS/Ti3C2Tx-O can generate pseudocapacitance-dominated storage behavior enabled by engineered surface reactions. As predicted, this electrode exhibits an enhanced Na storage capacity of 565 mAh g−1 at 0.1 A g−1 after 75 cycles, outperforming SnS/Ti3C2Tx-H (336 mAh g−1), SnS (212 mAh g−1), and Ti3C2Tx (104 mAh g−1) electrodes. 相似文献
66.
Dr. Saud Asif Ahmed Qiao-Bo Liao Qi Shen Dr. Mirza Muhammad Faran Ashraf Baig Juan Zhou Cai-Feng Shi Dr. Pir Muhammad Dr. Sumaira Hanif Prof. Kai Xi Prof. Xing-Hua Xia Prof. Kang Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(57):12996-13001
Layered/two-dimensional covalent organic frameworks (2D COF) are crystalline porous materials composed of light elements linked by strong covalent bonds. Interlayer force is one of the main factors directing the formation of a stacked layer structure, which plays a vital role in the stability, crystallinity, and porosity of layered COFs. The as-developed new way to modulate the interlayer force of imine-linked 2D TAPB-PDA-COF (TAPB = 1,3,5-tris(4-aminophenyl)benzene, PDA = terephthaldehyde) by only adjusting the pH of the solution. At alkaline and neutral pH, the pore size of the COF decreases from 34 Å due to the turbostratic effect. Under highly acidic conditions (pH 1), TAPB-PDA-COF shows a faster and stronger turbostratic effect, thus causing the 2D structure to exfoliate. This yields bulk quantities of an exfoliated few/single-layer 2D COF, which was well dispersed and displayed a clear Tyndall effect (TE). Furthermore, nanopipette-based electrochemical testing also confirms the slipping of layers with increase towards acidic pH. A model of pH-dependent layer slipping of TAPB-PDA-COF was proposed. This controllable pH-dependent change in the layer structure may open a new door for potential applications in controlled gas adsorption/desorption and drug loading/releasing. 相似文献
67.
Dr. Yongliang Zhang Botao Wu Dr. Mingdong Zhong Prof. Dr. Wen-Xiong Zhang Prof. Dr. Zhenfeng Xi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16472-16479
Transition-metal alkylidenes have exhibited wide applications in organometallic chemistry and synthetic organic chemistry, however, cyclic Schrock-carbene-like bis-alkylidenes of group 4 metals with a four-electron donor from an alkylidene have not been reported. Herein, the synthesis and characterization of five-membered cyclic bis-alkylidenes of titanium ( 4 a , b ) and zirconium ( 5 a , b ) are reported, as the first well-defined group 4 metallacyclopentatrienes, by two-electron reduction of their corresponding titana- and zirconacyclopentadienes. DFT analyses of 4 a show a four-electron donor (σ-donation and π-donation) from an alkylidene carbon to the metal center. The reaction of 4 a with N,N′-diisopropylcarbodiimide (DIC) leads to the [2+2]-cycloaddition product 6 . Compound 4 a reacted with CO, affording the oxycyclopentadienyl titanium complex 7 . These reactivities demonstrate the multiple metal–carbon bond character. The reactions of 4 a or 5 a with cyclooctatetraene (COT) or azobenzene afforded sandwich titanium complex 8 or diphenylhydrazine-coordinated zirconacyclopentadiene 9 , respectively, which exhibit two-electron reductive ability. 相似文献
68.
69.