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High‐Nuclear Organometallic Copper(I)–Alkynide Clusters: Thermochromic Near‐Infrared Luminescence and Solution Stability 下载免费PDF全文
Hong‐Yan Zhuo Dr. Hai‐Feng Su Zhao‐Zhen Cao Wei Liu Prof. Shu‐Ao Wang Lei Feng Dr. Gui‐Lin Zhuang Dr. Shui‐Chao Lin Prof. Mohamedally Kurmoo Prof. Chen‐Ho Tung Dr. Di Sun Prof. Lan‐Sun Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17619-17626
Cu(CF3COO)2 reacts with tert‐butylacetylene (tBuC≡CH) in methanol in the presence of metallic copper powder to give two air‐stable clusters, [CuI15(tBuC≡C)10(CF3COO)5]?tBuC≡CH ( 1 ) and [CuI16(tBuC≡C)12(CF3COO)4(CH3OH)2] ( 2 ). The assembly process involves in situ comproportionation reaction between Cu2+ and Cu0 and the formation of two different clusters is controlled by reactants concentration. The clusters consist of Cu15 and Cu16 cores co‐stabilized by strong by σ‐ and π‐bonded tert‐butylethynide and CF3COO? (together with methanol molecule in 2 ). Their stabilities in solution were confirmed using electrospray ionization mass spectrometry in which the cluster core remains intact for 1 in chloroform and acetone, and for 2 in acetonitrile. Strong thermochromic luminescence in the near infrared (NIR) region was observed in the solid‐state. Of particular interest, the emission maximum of 1 is red‐shifted from 710 nm at 298 K to 793 nm at 93 K, along with a 17‐fold fluorescence enhancement. In contrast, 2 exhibits red shift from 298 to 123 K followed by blue shift from 123 to 93 K. The emission wavelength was correlated with the structural parameters using variable‐temperature X‐ray single‐crystal analyses. The rich cuprophilic interaction plays a significant role in the formation of 3LMCT (tBuC≡C→Cux) excited state mixed with cluster‐centered (3CC) characters, which can be considerably influenced by temperature, leading to thermochromic luminescence. The present work provides 1) a new synthetic protocol for the high‐nuclear CuI–alkynyl clusters; 2) a comprehensive insight into the mechanism of thermochromic luminescence; 3) unusual emissive materials with the characters of NIR and thermochromic luminescence simultaneously. 相似文献
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Effect of polyethylene glycol on the crystallization and impact properties of polylactide‐based blends 下载免费PDF全文
Polylactide (PLA) was plasticized by polyethylene glycols (PEGs) with five different molecular weights (Mw = 200–20,000 g/mol). The effects of content and molecular weight of PEG on the crystallization and impact properties of PLA were studied by wide‐angle X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, transmission electron microscopy, and V‐notched impact tests, respectively. The results revealed that PEG‐10,000 could significantly improve the crystallization capacity and impact toughness of PLA. When the PEG‐10,000 content ranged from 0 to 20 wt%, the increases in both V‐notched Izod and Charpy impact strengths of PLA/PEG‐10,000 blends were 206.10% and 137.25%, respectively. Meanwhile, the crystallinity of PLA/PEG‐10,000 blends increased from 3.95% to 43.42%. For 10 wt% PEG content, the crystallization and impact properties of PLA/PEG blends mainly depended upon PEG molecular weight. With increasing the Mw of PEG, the crystallinity and impact strength of PLA/PEG blends first decreased and then increased. The introduction of PEG reduced the intermolecular force and enhanced the mobility of PLA chains, thus improving the crystallization capacity and flexibility of PLA. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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在混合溶剂中通过"grafting to"的方法将2种分子量不同的聚乙二醇单甲醚(MPEG M_w=750,4000)接枝到氨基修饰的St?ber法二氧化硅(SiO_2-NH_2)表面,制备双分布纳米接枝复合物.采用二步法,先将带环氧端基的低分子量聚乙二醇单甲醚(MPEG-EO)与SiO_2-NH_2在甲苯溶剂中充分反应后,与高分子量的MPEG-EO在甲苯和正癸烷的混合溶剂中使用相同的反应条件和后处理方法,能便捷制备出具有双分布接枝的纳米复合物.在接枝反应体系中,分子链的链段尺寸和接枝密度之间存在着密切关系.一定的范围内,接枝密度随链段尺寸减小而增大.通过改变混合溶剂比例来调控接枝链段的尺寸,可以很好控制聚合物的接枝密度.在双分布接枝的纳米复合物中,低分子量的接枝密度为0.85 chains/nm~2,高分子量的接枝密度能达到0.40 chains/nm~2,体现出了简单、高效、可控的特点,与聚环氧乙烷(PEO)共混后分散良好,对于制备出均匀分散的纳米复合材料起到了一定的指导作用. 相似文献
5.
Li-Zhao Huang Yue Shui Wei Chen Zhong-Ming Li Hong-Tao Song Guang-Ai Sun Jia-Zhuang Xu Gan-Ji Zhong Dong Liu 《高分子科学》2021,39(3):365-376
The correlation between aggregates and bound rubber structures in silicone rubbers(S(phr)) with various silica fractions(ΦSi) has been investigated by contrast matching small-angle neutron scattering(SANS), swelling kinetics, and low-field nuclear magnetic resonance(NMR).Mixed solvents with deuterated cyclohexane fractions of 4.9% and 53.7% were chosen to match the scattering length densities of the matrix(SMP(phr)) and the filler(SMS(phr)), respectively. All the data consistently suggest that:(i) There is a critical threshold ΦSic between 10 and 30 phr;below ΦSic, the isolated aggregates are dominant, while beyond ΦSic, some rubber fraction is trapped among the agglomerate;(ii) ΦSiindependent thicknesses around 7.5 nm(NMR) and 8.6 nm(SANS) suggest that the bound rubber formation is determined by inherent properties of the components, and the power-law around 4.2 suggests an exponential changed gradient density of the bound rubber;(iii) SMS(80) presents a bicontinuous bound rubber with three characteristic lengths of 41, 100, and 234 nm. The expanded correlation length, a 20 nm smaller aggregate sizes suggest that such existent bicontinuous network in dry samples with less ΦSi is kind of impacted by swelling. With the obtained bound rubber models, the reinforcing mechanism of filled silicone rubber is elucidated. 相似文献
6.
Hechong Chen Zehong Liang Xinyue Wang Yong Zhang Lingling Shui Dongmei Deng 《Annalen der Physik》2023,535(1):2200375
By applying a virtual source method, the exact and the paraxial solutions of the Swallowtail beams (SBs) that are governed by the inhomogeneous Helmholtz equation are introduced. The paraxial SBs generated experimentally possess both self-accelerating and self-focusing features. The parameters controlling the field distributions are discussed in theory. From the spectral representation of the Swallowtail wave, in the appropriate limit, the first four terms of the nonparaxial correction series for the (1+2)-dimensional Swallowtail waves that simplify to the SBs are obtained. 相似文献
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Ultra-cold atoms provide ideal platforms for interferometry.The macroscopic matter-wave property of ultra-cold atoms leads to large coherent length and long coherent time,which enable high accuracy and sensitivity to measurement.Here,we review our efforts to improve the performance of the interferometer.We demonstrate a shortcut method for manipulating ultra-cold atoms in an optical lattice.Compared with traditional ones,this shortcut method can reduce the manipulation time by up to three orders of magnitude.We construct a matter-wave Ramsey interferometer for trapped motional quantum states and significantly increase its coherence time by one order of magnitude with an echo technique based on this method.Efforts have also been made to enhance the resolution by multimode scheme.Application of a noise-resilient multi-component interferometer shows that increasing the number of paths could sharpen the peaks in the time-domain interference fringes,which leads to a resolution nearly twice compared with that of a conventional double-path two-mode interferometer.With the shortcut method mentioned above,improvement of the momentum resolution could also be fulfilled,which leads to atomic momentum patterns less than 0.6hkL. To identify and remove systematic noises,we introduce the methods based on the principal component analysis (PCA) that reduce the noise in detection close to the 1/√2 of the photon-shot noise and separate and identify or even eliminate noises.Furthermore,we give a proposal to measure precisely the local gravity acceleration within a few centimeters based on our study of ultracold atoms in precision measurements. 相似文献
9.
Zi-Qi Zhou Qi-Rui Shui Prof. Rui-Biao Fu Yuan-Bin Fang Prof. Zu-Ju Ma Prof. Xin-Tao Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(51):12976-12980
The discovery of new nonlinear optical (NLO) crystals with excellent properties is in urgently demand because of their ability to generate coherent light. Herein, we report an unique NLO lead bromide formate, KCs2[Pb2Br5 (HCOO)2], which has been synthesized by a mix-solvothermal method. KCs2[Pb2Br5(HCOO)2] exhibits strong phase-matching second-harmonic generation (SHG) response (6.5×KDP), large birefringence (0.16@ 1064 nm), and a wide transparent window in most visible light and mid-IR region. Interestingly, KCs2[Pb2Br5(HCOO)2] features a polar 3D lead-bromide framework in which adjacent Pb−Br layers containing coplanar Pb6Br6 rings are not only parallel to each other, but also orient in the same direction. These oriented arrangements are responsible for the strong SHG response and large birefringence that are elucidated by both local dipole moment and theoretical calculations. This research provides a new strategy to explore subsequent NLO crystals. 相似文献
10.
Cao Ding Dong Yingying Tang Ying Ye Yaoyao Hu Shui Guo Zhenguo Li Xinhua 《Catalysis Surveys from Asia》2021,25(4):437-444
Catalysis Surveys from Asia - A facile and efficient electrocatalyst for hydrogen evolution reaction (HER) to produce hydrogen is very important for future energy. In this paper, amorphous... 相似文献