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861.
Two‐Coordinate Iron(I) Complex [Fe{N(SiMe3)2}2]−: Synthesis,Properties, and Redox Activity
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Dr. C. Gunnar Werncke Philip C. Bunting Dr. Carine Duhayon Prof. Jeffrey R. Long Dr. Sébastien Bontemps Dr. Sylviane Sabo‐Etienne 《Angewandte Chemie (International ed. in English)》2015,54(1):245-248
First‐row two‐coordinate complexes are attracting much interest. Herein, we report the high‐yield isolation of the linear two‐coordinate iron(I) complex salt [K(L)][Fe{N(SiMe3)2}2] (L=18‐crown‐6 or crypt‐222) through the reduction of either [Fe{N(SiMe3)2}2] or its three‐coordinate phosphine adduct [Fe{N(SiMe3)2}2(PCy3)]. Detailed characterization is gained through X‐ray diffraction, variable‐temperature NMR spectroscopy, and magnetic susceptibility studies. One‐ and two‐electron oxidation through reaction with I2 is further found to afford the corresponding iodo iron(II) and diiodo iron(III) complexes. 相似文献
862.
用密度泛函理论结合全电子自旋极化方法构建并优化出了最稳定的(Al16Ti)n± (n=0-3)离子团簇, 研究了其几何结构、稳定性和电子结构. 同时研究了水分子在(Al16Ti)n± (n=0-3)离子团簇表面的吸附结构和吸附能. 研究结果与纯(Al17Ti)n± (n=0-3)离子团簇的电子结构及其与H2O分子的相互作用规律做了对比. 通过电子最高占据轨道和最低空轨道的空间分布, 发现大部分的活性电子占据在Ti 原子位置, 少量电子根据曲率从大到小的顺序依次占据. 通过分析最稳定的(Al16TiH2O)n± (n=0-3)吸附化合物的几何结构可以看出, 水分子都倾向于吸附在Ti原子上, 并且为亲氧吸附. 在所有的吸附化合物中, (Al16TiH2O)+具有最短的平均O―H键长, 比孤立H2O分子中的O―H键约长0.0003 nm, 然后随着电子数的增加或减少, O―H键都会进一步被拉长. 研究结果表明, Al 团簇离子中Ti 原子的掺杂可以有效提高H2O分子的解离效率. 另外, 在金属团簇的几何结构效应与杂质效应共同出现时, 杂质的影响占据了主导地位. 相似文献
863.
Molecular Dynamics Simulation Study of ClF in Water: Halogen Bonding Interaction in Liquid
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Does the halogen bonding interaction co-exist in liquid when it competes with the hydrogen bonding interaction? The classical molecular dynamics simulations for the solvation properties of ClF molecule in water are performed with the Lennard-Jones plus Coulomb electrostatic potential parameters that are optimized with ab initio interaction energy calculations for the pre-reactive H2O…ClF complex. We find that the halogen bonding interactions occur between O and Cl atoms and have the comparable strength and population with respect to the hydrogen bonding interactions of Cl…H. 相似文献
864.
采用密度泛函理论方法对以四硫富瓦烯(TTF)为端基、 苯乙烯为桥的5种不同中心核(富电子核: 氮、 三聚咔唑及三聚吲哚; 缺电子核: 三嗪及三聚喹喔啉)构成的星型三支D-π-A型化合物的几何结构、 电子吸收光谱及电荷转移性质进行了研究. 结果表明, 通过改变中心核的类型, 可有效调节LUMO能级, 改变能隙的大小. 电荷差分密度及跃迁密度矩阵分析结果表明, 两支内的TTF端基与核到共轭桥链的电荷转移跃迁及少量的π→π*跃迁对高能吸收带有贡献; 缺电子核化合物的低能吸收峰主要是TTF端基到桥链和中心核的电荷转移跃迁贡献, 不同于富电子核化合物明显的TTF贡献的支内定域电荷转移跃迁. 重组能计算表明, 除化合物NST(中心核为氮)外, 其余4个化合物的空穴重组能(λh)与电子重组能(λe)相当, 中心核为三聚咔唑的化合物CST重组能相对较小. 相似文献
865.
Annaliese E. Thuijs George Christou Khalil A. Abboud 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(3):185-187
The title dodecanuclear Mn complex, namely dodeca‐μ2‐acetato‐κ24O:O′‐tetraaquatetra‐μ2‐nitrato‐κ8O:O′‐tetra‐μ4‐oxido‐octa‐μ3‐oxido‐tetramanganese(IV)octamanganese(III) nitromethane tetrasolvate, [Mn12(CH3COO)12(NO3)4O12(H2O)4]·4CH3NO2, was synthesized by the reaction of Mn2+ and Ce4+ sources in nitromethane with an excess of acetic acid. This compound is distinct from the previously known single‐molecule magnet [Mn12O12(O2CMe)16(H2O)4], synthesized by Lis [Acta Cryst. (1980), B 36 , 2042–2044]. It is the first Mn12‐type molecule containing nitrate ligands to be directly synthesized without the use of a preformed cluster. Additionally, this molecule is distinct from all other known Mn12 complexes due to intermolecular hydrogen bonds between the nitrate and water ligands, which give rise to a three‐dimensional network. The complex is compared to other known Mn12 molecules in terms of its structural parameters and symmetry. 相似文献
866.
以N-烷基咔唑作为电子给体和共轭桥中心, 二米基硼作为端基电子受体, 合成了两个V形A-π-D-π-A型新化合物: 3,6-二{[(E)-2-(5-二米基硼)噻吩]乙烯基}-N-丁基-咔唑 {N-butyl-3,6-bis{(E)-2-[5-(dimesitylboryl)thiophen-2-yl]-vinyl}-carbazole, BBTC}和3,6-二[(E)-(4-二米基硼)苯乙烯基]-N-己基-咔唑, {N-hexyl-3,6-bis[(E)-4-(dimesitylboryl)-styryl]-carbazole, BBSC}. 这两个化合物在蓝绿光波段都有较强的荧光发射. 光谱数据表明, 扩大共轭体系并在端基引入含硼基团导致吸收谱和发射谱显著红移, 并增大分子内电荷转移. 相似文献
867.
Oshio H Nihei M Yoshida A Nojiri H Nakano M Yamaguchi A Karaki Y Ishimoto H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(3):843-848
The reaction of 1/3 equivalent of CuCl2.2H2O with MnCl2.4H2O and 5-bromo-2-salicylideneamino-1-propanol (H(2)5-Br-sap) in methanol gave dark brown crystals of [MnIIICuIICl(5-Br-sap)2(MeOH)] (1). Complex 1 has an alkoxo-bridged dinuclear core of MnIII and CuII ions, which have elongated octahedral and square-planar coordination geometries, respectively. In dc magnetic susceptibility measurements, chi(m)T values increased as the temperature was lowered, followed by a sudden decrease below 20 K. This behavior is indicative of the occurrence of intramolecular ferromagnetic interactions, and fitting gave an S=5/2 spin ground state with an exchange coupling constant J(MnCu) of +78 cm(-1). Magnetization data collected as a function of temperature and applied magnetic field were analyzed by using a spin Hamiltonian with isotropic Zeeman and axial zero-field splitting (ZFS) terms, and a negative D(5/2) value (-1.86 cm(-1)) was obtained. A high-field EPR (HFEPR) spectrum (342.0 GHz) at 4.2 K was composed of four peaks, and two additional peaks at higher magnetic field appeared as the temperature was increased. The temperature dependences in the HFEPR spectra are indicative of a negative D(5/2) value, and fitting of the data gave D(5/2)=-1.81 cm(-1). In the ac magnetic susceptibility measurements, frequency dependent in-phase (chi(m)') and out-of-phase (chi(m)') signals with peak maxima at 0.7-1.5 K were observed and small peaks below 0.7 K appeared. The ac susceptibility data supports that 1 is a single-molecule magnet (SMM). Arrhenius plots for the chi(m)' peaks from 0.7-1.5 K gave the re-orientation energy barrier (DeltaE) of 10.5 K with a pre-exponential factor of 8.2x10(-8) s. 相似文献
868.
869.
Techniques in single-molecule fluorescence spectroscopy now allow sophisticated studies of photophysical processes in single molecules. As interest grows in the possibilities of molecular electronics, researchers have begun to turn these techniques to the study of electron transfer. Electron-transfer reactions have now been detected and measured at the single-molecule level in a variety of systems and on a variety of timescales by adapting techniques from previous single-molecule fluorescence studies. 相似文献
870.
Ruiyan Li Zhiru Li Di Wu Xiyun Hao Rujiao Li Chiachung Sun 《International journal of quantum chemistry》2005,103(3):299-307
Using four basis sets, 6‐311G(d,p), 6‐31+G(d,p), 6‐311++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for dimers CH2O? HF, CH2O? H2O, CH2O? NH3, and CH2O? CH4. The structures of CH2O? HF, CH2O? H2O, and CH2O? NH3 are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the acidic H atoms of CH2O and lone pair(s) on the F atom in HF, the O atom in H2O, or the N atom in NH3. By contrast with above the three dimers, for CH2O? CH4, because there is not a π‐type hydrogen‐bond to bend its linear hydrogen bond, the structure of CH2O? CH4 is a noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD(T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献