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1.
Feng Cheng Shuqi Wu Wenwei Zheng Shengqun Su Takumi Nakanishi Wenhuang Xu Pritam Sadhukhan Hibiki Sejima Shimon Ikenaga Kaoru Yamamoto Kaige Gao Shinji Kanegawa Prof. Osamu Sato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202161
The crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non-ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P21). The polarization of the crystals along the b-axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature. 相似文献
2.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
3.
Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand 下载免费PDF全文
Zhengran Wang 《中国物理 B》2022,31(4):48202-048202
Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH2) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S0 and S1 states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH2 can undergo the ESDPT process in the S1 state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules. 相似文献
4.
Maria Eduarda B. S. de Oliveira Adilson Sartoratto Jean Carlos Cardoso 《Molecules (Basel, Switzerland)》2020,25(24)
The efficient production of plant-derived medicinal compounds (PDMCs) from in vitro plants requires improvements in knowledge about control of plant or organ development and factors affecting the biosynthesis pathway of specific PDMCs under in vitro conditions, leading to a realistic large-scale tool for in vitro secondary metabolite production. Thus, this study aimed to develop an in vitro technique, through the induction and proliferation of calli, for production of plant fresh weight, and to compare the PDMC profile obtained from the plants versus in vitro calli of Phyllanthus amarus. It was successfully possible to obtain and proliferate two types of calli, one with a beige color and a friable appearance, obtained in the dark using Murashige and Skoog (MS) medium plus 2,4-dichlorophenoxyacetic acid (2,4-D), and a second type with a green color, rigid consistency, and nonfriable appearance obtained under light conditions and MS medium plus 6-benzyladenine (6-BA). In vitro micropropagated plants that gave rise to calli were also acclimatized in a greenhouse and cultivated until obtaining the mass for PDMC analysis and used as a control. While the micropropagated-derived plants concentrated the lignans niranthin, nirtetralin, and phyllanthin, the Phyllanthus amarus calli proliferated in vitro concentrated a completely different biochemical profile and synthesis of compounds, such as betulone, squalene, stigmasterol, and β-sitosterol, in addition to others not identified by GC-MS database. These results demonstrate the possibility of applying the calli in vitro from Phyllanthus amarus for production of important PDMCs unlike those obtained in cultures of differentiated tissues from field plants. 相似文献
5.
Yong-Jin Zhao Jian-Ping Ma Jianzhong Fan Yan Geng Yu-Bin Dong 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(6):605-615
The tridentate organic ligand 4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoic acid ( H3L ) has been synthesized (as the methanol 1.25‐solvate, C48H39NO6·1.25CH3OH). As a donor–acceptor motif molecule, H3L possess strong intramolecular charge transfer (ICT) fluorescence. Through hydrogen bonds, H3L molecules construct a two‐dimensional (2D) network, which pack together into three‐dimensional (3D) networks with an ABC stacking pattern in the crystalline state. Based on H3L and M(NO3)2 salts (M = Cd and Zn) under solvothermal conditions, two metal–organic frameworks (MOFs), namely, catena‐poly[[triaquacadmium(II)]‐μ‐10‐(4‐carboxyphenyl)‐4,4′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6‐diyl)dibenzoato], [Cd(C48H37NO6)(H2O)3]n, I , and poly[[μ3‐4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoato](μ3‐hydroxido)zinc(II)], [Zn2(C48H36NO6)(OH)]n, II , were synthesized. Single‐crystal analysis revealed that both MOFs adopt a 3D structure. In I , partly deprotonated HL 2? behaves as a bidentate ligand to link a CdII ion to form a one‐dimensional chain. In the solid state of I , the existence of weak interactions, such as O—H…O hydrogen bonds and π–π interactions, plays an essential role in aligning 2D nets and 3D networks with AB packing patterns for I . The deprotonated ligand L 3? in II is utilized as a tridentate building block to bind ZnII ions to construct 3D networks, where unusual Zn4O14 clusters act as connection nodes. As a donor–acceptor molecule, H3L exhibits fluorescence with a photoluminescence quantum yield (PLQY) of 70% in the solid state. In comparison, the PL of both MOFs is red‐shifted with even higher PLQYs of 79 and 85% for I and II , respectively. 相似文献
6.
Dr. Aleksandra Markovic Luca Gerhards Dr. Pia Sander Dr. Carsten Dosche Prof. Dr. Thorsten Klüner Prof. Dr. Rüdiger Beckhaus Prof. Gunther Wittstock 《Chemphyschem》2020,21(22):2506-2514
Multinuclear transition metal complexes bridged by ligands with extended π-electronic systems show a variety of complex electronic transitions and electron transfer reactions. While a systematic understanding of the photochemistry and electrochemistry has been attained for binuclear complexes, much less is known about trinuclear complexes such as hexaphenyl-5,6,11,12,17,18-hexaazatrinaphthylene-tristitanocene [(Cp2Ti)3HATN(Ph)6]. The voltammogram of [(Cp2Ti)3HATN(Ph)6] shows six oxidation and three reduction waves. Solution spectra of [(Cp2Ti)3HATN(Ph)6] and of the electrochemically formed oxidation products show electronic transitions in the UV, visible and the NIR ranges. Density functional theory (DFT) and linear response time-dependent DFT show that the three formally titanium(II) centers transfer an electron to the HATN ligand in the ground state. The optically excited transitions occur exclusively between ligand-centered orbitals. The charged titanium centers only provide an electrostatic frame to the extended π-electronic system. Complete active self-consistent field (CASSCF) calculation on a structurally simplified model compound, which considers the multi-reference character imposed by the three titanium centers, can provide an interpretation of the experimentally observed temperature-dependent magnetic behavior of the different redox states of the title compound in full consistency with the interpretation of the electronic spectra. 相似文献
7.
Palladium‐Catalyzed Direct C2‐Arylation of an N‐Heterocyclic Carbene: An Atom‐Economic Route to Mesoionic Carbene Ligands 下载免费PDF全文
Dr. Rajendra S. Ghadwal Sven O. Reichmann Dr. Regine Herbst‐Irmer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4247-4251
Blocking the C2 position of an imidazole‐derived classical N‐heterocyclic carbene (NHC) with an aryl group is an essential strategy to establish a route to mesoionic carbenes (MICs), which coordinate to the metal via the C4 (or C5) carbon atom. An efficient catalytic route to MIC precursors by direct arylation of an NHC is reported. Treatment of 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr) with an aryl iodide (RC6H4I) in the presence of 0.5 mol % of [Pd2(dba)3] (dba=dibenzylideneacetone) precatalyst affords the C2‐arylated imidazolium salts {IPr(C6H4R)}I (R=H, 4‐Me, 2‐Me, 4‐OMe, 4‐COOMe) in excellent (up to 92 %) yields. Treatment of {IPr(C6H5)}I with CuI and KN(SiMe3)2 exclusively affords the MIC–copper complex [(IPrPh)CuI]. 相似文献
8.
9.
Corrigendum: Reactions with a Metalloid Tin Cluster {Sn10[Si(SiMe3)3]4}2−: Ligand Elimination versus Coordination Chemistry 下载免费PDF全文
10.
Inside Cover: Bio‐Inspired Transition Metal–Organic Hydride Conjugates for Catalysis of Transfer Hydrogenation: Experiment and Theory (Chem. Eur. J. 7/2015) 下载免费PDF全文