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31.
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
32.
Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes 下载免费PDF全文
Guo‐Ling Li Dr. Shinji Kanegawa Dr. Zi‐Shuo Yao Dr. Sheng‐Qun Su Shu‐Qi Wu Dr. You‐Gui Huang Dr. Soonchul Kang Prof. Dr. Osamu Sato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17130-17135
Two polymorphic structures have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs showed distinct thermal‐ and photomagnetic behavior, and are thus ideal for studying the “pure” intermolecular factors to VT transitions. In polymorph 1A , the VT cations are arranged head‐to‐waist with their neighbors and exhibit weak π???π interactions, resulting in a gradual and incomplete thermal VT transition. In contrast, the cations in polymorph 1B are arranged head‐to‐tail and exhibit relatively strong π???π interactions, leading to an abrupt and complete thermal VT transition with adjustable hysteresis loop at around room temperature. The VT process for both polymorphs can be induced by light, but the light‐excited state of 1B? 2H2O has a higher thermal relaxation temperature than that of 1A? 3H2O. 相似文献
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34.
Shi‐Chao Wei Dr. Mei Pan Yuan‐Zhong Fan Haoliang Liu Prof. Jianyong Zhang Prof. Cheng‐Yong Su 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7418-7427
Creating cavities in varying levels, from molecular containers to macroscopic materials of porosity, have long been motivated for biomimetic or practical applications. Herein, we report an assembly approach to multiresponsive supramolecular gels by integrating photochromic metal–organic cages as predefined building units into the supramolecular gel skeleton, providing a new approach to create cavities in gels. Formation of discrete O‐Pd2L4 cages is driven by coordination between Pd2+ and a photochromic dithienylethene bispyridine ligand (O‐PyFDTE). In the presence of suitable solvents (DMSO or MeCN/DMSO), the O‐Pd2L4 cage molecules aggregate to form nanoparticles, which are further interconnected through supramolecular interactions to form a three‐dimensional (3D) gel matrix to trap a large amount of solvent molecules. Light‐induced phase and structural transformations readily occur owing to the reversible photochromic open‐ring/closed‐ring isomeric conversion of the cage units upon UV/visible light radiation. Furthermore, such Pd2L4 cage‐based gels show multiple reversible gel–solution transitions when thermal‐, photo‐, or mechanical stimuli are applied. Such supramolecular gels consisting of porous molecules may be developed as a new type of porous materials with different features from porous solids. 相似文献
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36.
Xiaoye Ma Chuanqing Kang Wenhui Chen Rizhe Jin Haiquan Guo Xuepeng Qiu Lianxun Gao 《Journal of polymer science. Part A, Polymer chemistry》2016,54(4):570-581
To investigate the influence of hydrogen bonding on the properties of polyimides (PIs) containing rigid rod‐like groups, five symmetrical diamines containing benzimidazole, benzoxazole, and hydroxy group were synthesized, and then a series of PIs were prepared. Results showed that hydroxyl‐containing poly(benzoxazole imide)s possess higher glass transition temperature (Tg) and dimensional stabilities than their corresponding poly(benzoxazole imide)s. Moreover, the corresponding poly(benzimidazole imide)s presented the best performances, such as the highest Tg, the highest char yield and the highest dimensional stabilities. The influence of hydrogen bonding of benzimidazole on the properties of PIs was stronger than that of hydroxyl groups. Hydroxyl‐containing poly(benzoxazole imide)s were formed in crosslinking structures after heat treatment at 400 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 570–581 相似文献
37.
We establish the construction theory of function based upon a local field K p as underlying space. By virture of the concept of pseudo-differential operator, we introduce "fractal calculus"(or, p-type calculus, or, Gibbs-Butzer calculus). Then, show the Jackson direct approximation theorems, Bermstein inverse approximation theorems and the equivalent approximation theorems for compact group D( Kp) and locally compact group K+p(= Kp), so that the foundation of construction theory of function on local fields is established. Moreover, the Jackson type, Bernstein type,and equivalent approximation theorems on the H ?lder-type space Cσ(Kp), σ 0, are proved; then the equivalent approximation theorem on Sobolev-type space Wrσ(Kp),σ≥ 0, 1 ≤ r +∞, is shown. 相似文献
38.
Readily Accessible and Predictable Naphthalene‐Based Two‐Photon Fluorophore with Full Visible‐Color Coverage 下载免费PDF全文
Ja Young Koo Cheol Ho Heo Dr. Young‐Hee Shin Dahahm Kim Dr. Chang Su Lim Prof. Dr. Bong Rae Cho Prof. Dr. Hwan Myung Kim Prof. Dr. Seung Bum Park 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14166-14170
Herein we report 22 acedan‐derived, two‐photon fluorophores with synthetic feasibility and full coverage of visible wavelength emission. The emission wavelengths were predicted by computational analysis, which enabled us to visualize multicolor images by two‐photon excitation with single wavelength, and to design a turn‐on, two‐photon fluorescence sensor for endogenous H2O2 in Raw 264.7 macrophage and rat brain hippocampus ex vivo. 相似文献
39.
Christian W. Pester Justin E. Poelma Benjaporn Narupai Shrayesh N. Patel Gregory M. Su Thomas E. Mates Yingdong Luo Christopher K. Ober Craig J. Hawker Edward J. Kramer 《Journal of polymer science. Part A, Polymer chemistry》2016,54(2):253-262
In an attempt to create a polymer brush-based platform for the systematic study for anti-biofouling surfaces, the benefits of surface initiated, visible light-mediated radical polymerization are utilized to fabricate well-defined, chemically ambiguously patterned surfaces. A variety of analytical tools are used to illustrate the precise tuning of surface chemistry and thoroughly characterize spatially well-defined, hydrophilic/hydrophobic surfaces composed of poly(ethylene glycol methacrylate) and poly(trifluoroethyl methacrylate) with chemical definition on the micron scale. Advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization are combined to achieve both high spatial control and expanded monomer tolerance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 253–262 相似文献
40.
Guo-Xing Li Xiao-Wei Qu Lu-Wei Hao Qing Li Su Chen 《Journal of polymer science. Part A, Polymer chemistry》2022,60(11):1710-1717
From the implementation point of view, the printable magnetic Janus colloidal photonic crystals (CPCs) microspheres are highly desirable. Herein, we developed a dispensing-printing strategy for magnetic Janus CPCs display via a microfluidics-automatic printing system. Monodisperse core/shell colloidal particles and magnetic Fe3O4 nanoparticles precursor serve as inks. Based on the equilibrium of three-phase interfacial tensions, Janus structure is successfully formed, followed by UV irradiation and self-assembly of colloid particle to generate magnetic Janus CPCs microspheres. Notably, this method shows distinct superiority with highly uniform Janus CPCs structure, where the TMPTA/Fe3O4 hemisphere is in the bottom side while CPCs hemisphere is in the top side. Thus, by using Janus CPCs microspheres with two different structural colors as pixel points, a pattern with red flower and green leaf is achieved. Moreover, 1D linear Janus CPCs pattern encapsulated by hydrogel is also fabricated. Both the color and the shape can be changed under the traction of magnets, showing great potentials in flexible smart displays. We believe this work not only offers a new feasible pathway to construct magnetic Janus CPCs patterns by a dispensing-printable fashion, but also provides new opportunities for flexible and smart displays. 相似文献