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191.
A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni(II)-Fe(III) complexes. The presence of steric bpb(2-) ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following J(NiFe) values (based on the spin exchange Hamiltonian H = -2J(NiFe) S(Ni) (S(Fe(1)) + S(Fe(2))): J(NiFe) = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm(-1), respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N[triple bond]C bond angle, the stronger the Ni- - -Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with T(N) = 3.5 K. Below T(N) (1.82 K), a metamagnetic behavior was observed with the critical field of approximately 6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials. 相似文献
192.
Dixit AA Lei Y Lee KW Quiñones E Houston PL 《The journal of physical chemistry. A》2005,109(9):1770-1775
Multiphoton excitation and dissociation of SO(2) have been investigated in the wavelength range from 224 to 232 nm. Strong evidence is found for two-photon excitation to the H Rydberg state, followed by dissociation to SO + O and ionization of the SO product by absorption of a third photon. The two-photon excitation is resonantly enhanced via the C (1)B(2) intermediate state, and the two-photon yield spectrum thus bears a strong resemblance to the spectrum of this intermediate. Imaging of the O((3)P(2)), S((1)D(2)), and SO products suggests that, following dissociation of SO(2) from the H state, SO is produced in the A and B electronic states. S((1)D(2)) is produced both from two-photon dissociation of SO(2) to give S((1)D(2)) + O(2) and by single-photon dissociation of SO(+). In the former process, the O(2) is likely formed in all of its lowest three electronic states. 相似文献
193.
Shan Qian Li Hai Lei Tang Jin Cheng Yang Yong Wu 《中国化学快报》2007,18(3):261-262
An optically active intermediate 5 for A-ring of 19-nor-1a,25-dihydroxyvitamin D3 2 has been synthesized in five steps, starting from readily available, inexpensive D( )-xylose 6 with good yield. 相似文献
194.
Recent advances on the deoximation reactions are reviewed in this review. It was shown that catalytic deoximation with molecular oxygen as the mild oxidant should be the developing trend of the reaction. 相似文献
195.
γ-[SiW10O36]8-夹心型稀土元素单取代多酸化合物的合成与表征 总被引:2,自引:0,他引:2
利用缺位填充法合成了12个γ-[SiW10O36]8-夹心型稀土元素单取代多酸化合物K13[Ln(SiW10O36)2]·nH2O(Ln=La3+,Ce3+,Pr3+,Nd3+,Sm3+,Eu3+,Gd3+,Tb3+,Dy3+,Ho3+,Er3+,Yb3+).通过元素分析确定其组成,由红外光谱、紫外-可见吸收光谱、循环伏安及室温磁化率测定结果确认稀土离子与γ-[SiW10O36]8-相配位;183WNMR及荧光光谱结果则表明,稀土离子处于2个γ-[SiW10O36]8-构成的八配位环境中,标题化合物具有夹心型D2d对称性结构. 相似文献
196.
Xianhao Lv Mizhen Sun Lei Xu Runzhe Wang Huayi Zhou Yuyu Pan Shitong Zhang Qikun Sun Shanfeng Xue Wenjun Yang 《Chemical science》2020,11(19):5058
Designing a donor–acceptor (D–A) molecule with a hybridized local and charge transfer (HLCT) excited state is a very effective strategy for producing an organic light-emitting diode (OLED) with a high exciton utilization efficiency and external quantum efficiency. Herein, a novel twisting D–π–A fluorescent molecule (triphenylamine–anthracene–phenanthroimidazole; TPAAnPI) is designed and synthesized. The excited state properties of the TPAAnPI investigated through photophysical experiments and density functional theory (DFT) analysis reveal that its fluorescence is due to the HLCT excited state. The optimized non-doped blue OLED using TPAAnPI as a light-emitting layer exhibits a novel blue emission with an electroluminescence (EL) peak at 470 nm, corresponding to the Commission International de L''Eclairage (CIE) coordinates of (0.15, 0.22). A fabricated device termed Device II exhibits a maximum current efficiency of 18.09 cd A−1, power efficiency of 12.35 lm W−1, luminescence of ≈29 900 cd cm−2, and external quantum efficiency (EQE) of 11.47%, corresponding to a high exciton utilization efficiency of 91%. Its EQE remains as high as 9.70% at a luminescence of 1000 cd m−2 with a low efficiency roll-off of 15%. These results are among the best for HLCT blue-emitting materials involved in non-doped blue fluorescent OLEDs. The performance of Device II highlights a great industrial application potential for the TPAAnPI molecule.A new pure fluorescent blue HLCT-emitter was designed and synthesized. Highly efficient non-doped blue OLEDs with low efficiency roll-off were achieved. 相似文献
197.
Huijuan Lu Lei Mei Gaoyong Zhang Xiaohai Zhou 《Journal of inclusion phenomena and macrocyclic chemistry》2007,59(1-2):81-90
The interaction between cucurbit[6]uril and N,N′-(m-bispyridinecarboxamide)-1,n-alkane (m = 2, 3, 4; n = 4, 6, 8) has been investigated by 1H-NMR, ESI-MS and single crystal X-ray diffraction method. The results show that cucurbit[6]uril can form pseudorotaxanes with N,N′-(m-bispyridinecarboxamide)-1,6-hexane (m = 2, 3, 4) easily. When the alkyl chain length increases (n = 8), the binding mode is identical, but the binding ability of the host towards guest decreases. In both two cases cucurbit[6]uril shows no selectivity towards positional isomers. However, in the case of n = 4, the binding mode is different, having relations with positional substitution of the guest. Only N,N′-(m-bispyridinecarboxamide)-1,4-butane (m = 2) can form pseudorotaxane with cucurbit[6]uril, while the other two (m = 3, m = 4) form external complex with cucurbit[6]uril. The possible reason for the difference has been discussed. 相似文献
198.
Lei Liu Wes Lee Mingbin Yuan Chris Acha Michael B. Geherty Brandon Williams Osvaldo Gutierrez 《Chemical science》2020,11(12):3146
Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. Mechanistic studies support the diffusion of alkyl radical intermediates out of the solvent cage to participate in an intra- or intermolecular radical cascade with a range of VCPs followed by re-entering the Fe radical cross-coupling cycle to undergo (stereo)selective C(sp2)–C(sp3) bond formation. This work provides a proof-of-concept of the use of vinyl cyclopropanes as synthetically useful 1,5-synthons in Fe-catalyzed conjunctive cross-couplings with alkyl halides and aryl/vinyl Grignard reagents. Overall, we provide new design principles for Fe-mediated radical processes and underscore the potential of using combined computations and experiments to accelerate the development of challenging transformations.Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. 相似文献
199.
A novel silicone and phosphate modified acrylate (DGTH) was synthesized and characterized by 1H NMR and FTIR. It was found that DGTH could be cured both by UV radiation and moisture mode with FTIR. The flammability and thermal behavior of the cured film were studied by the limited oxygen index (LOI), thermogravimetric analysis (TG) and real time Fourier transform infrared (RT-FTIR). The LOI value of the cured film is 48 and the TG data shows that the cured film has three characteristic degradation temperature regions, attributing to the decomposition of phosphate and polyurethane to alcohols and isocyanates, thermal pyrolysis of alkyl chains, and decomposition of unstable structures in char, respectively. The RT-FTIR data implies that the degraded products of phosphate form poly(phosphoric acid) further catalyse the breakage of carbonyl groups to form an intumescent char, preventing the samples from further burning. 相似文献