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991.
Gadolinium(III)‐Hydroxy Ladders Trapped in Succinate Frameworks with Optimized Magnetocaloric Effect
Yan‐Cong Chen Fu‐Sheng Guo Prof. Dr. Yan‐Zhen Zheng Jun‐Liang Liu Ji‐Dong Leng Róbert Tarasenko Prof. Dr. Martin Orendáč Dr. Jan Prokleška Prof. Dr. Vladimír Sechovský Prof. Dr. Ming‐Liang Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13504-13510
Two kinds of inorganic gadolinium(III)‐hydroxy “ladders”, [2×n] and [3×n], were successfully trapped in succinate (suc) coordination polymers, [Gd2(OH)2(suc)2(H2O)]n ? 2n H2O ( 1 ) and [Gd6(OH)8(suc)5(H2O)2]n ? 4n H2O ( 2 ), respectively. Such coordination polymers could be regarded as alternating inorganic–organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (ΔH=70 kG) 42.8 J kg?1 K?1 for complex 1 and 48.0 J kg?1 K?1 for complex 2 . The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm?3 K?1 for complexes 1 and 2 , respectively. 相似文献
992.
Yong‐Jun Bian Chao‐Yue Chen Prof. Zhi‐Zhen Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1129-1133
An efficient palladium‐catalyzed C? H functionalization of aldehydes with various N‐substituted N‐heteroarene‐2‐carboxamides has been developed for the synthesis of secondary imides. The reaction tolerates various functionalities, such as methoxy, fluoro, chloro, and bromo groups. A tentative radical mechanism for a PdII/PdIV catalytic cycle is proposed. 相似文献
993.
Dr. Peng Cui Dr. Thomas P. Spaniol Prof. Dr. Laurent Maron Prof. Dr. Jun Okuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13437-13444
The rare‐earth‐metal? hydride complexes [{(1,7‐Me2TACD)LnH}4] (Ln=La 1 a , Y 1 b ; (1,7‐Me2TACD)H2=1,7‐dimethyl‐1,4,7,10‐tetraazacyclododecane, 1,7‐Me2[12]aneN4) were synthesized by hydrogenolysis of [{(1,7‐Me2TACD)Ln(η3‐C3H5)}2] with 1 bar H2. The tetrameric structures were confirmed by 1H NMR spectroscopy and single‐crystal X‐ray diffraction of compound 1 a . Both complexes catalyze the dehydrogenation of secondary amine? borane Me2NH ? BH3 to afford the cyclic dimer (Me2NBH2)2 and (Me2N)2BH under mild conditions. Whilst the complete conversion of Me2NH ? BH3 was observed within 2 h with lanthanum? hydride 1 a , the yttrium homologue 1 b required 48 h to reach 95 % conversion. Further reactions of compound 1 a with Me2NH ? BH3 in various stoichiometric ratios gave a series of intermediate products, [{(1,7‐Me2TACD)LaH}4](Me2NBH2)2 ( 2 a ), [(1,7‐Me2TACDH)La(Me2NBH3)2] ( 3 a ), [(1,7‐Me2TACD)(Me2NBH2)La(Me2NBH3)] ( 4 a ), and [(1,7‐Me2TACD)(Me2NBH2)2La(Me2NBH3)] ( 5 a ). Complexes 2 a , 3 a , and 5 a were isolated and characterized by multinuclear NMR spectroscopy and single‐crystal X‐ray diffraction studies. These intermediates revealed the activation and coordination modes of “Me2NH ? BH3” fragments that were trapped within the coordination sphere of a rare‐earth‐metal center. 相似文献
994.
Dr. Qiu‐Feng Lü Jia‐Yin Zhang Jun Yang Zhi‐Wei He Prof. Dr. Chang‐Qing Fang Qilang Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):10935-10944
Self‐assembled poly(N‐methylaniline)–lignosulfonate (PNMA–LS) composite spheres with reactive silver‐ion adsorbability were prepared from N‐methylaniline by using lignosulfonate (LS) as a dispersant. The results show that the PNMA–LS composite consisted of spheres with good size distribution and an average diameter of 1.03–1.27 μm, and the spheres were assembled by their final nanofibers with an average diameter of 19–34 nm. The PNMA–LS composite spheres exhibit excellent silver‐ion adsorption; the maximum adsorption capacity of silver ions is up to 2.16 g g?1 at an adsorption temperature of 308 K. TEM and wide‐angle X‐ray results of the PNMA–LS composite spheres after absorption of silver ions show that silver ions are reduced to silver nanoparticles with a mean diameter of about 11.2 nm through a redox reaction between the PNMA–LS composite and the silver ions. The main adsorption mechanism between the PNMA–LS composite and the silver ions is chelation and redox adsorption. In particular, a ternary PNMA–LS–Ag composite achieved by using the reducing reaction between PNMA–LS composite spheres and silver ions can be used as an antibacterial material with high bactericidal rate of 99.95 and 99.99 % for Escherichia coli and Staphylococcus aureus cells, respectively. 相似文献
995.
996.
Kazuhiko Semba Masataka Shinomiya Prof. Dr. Tetsuaki Fujihara Prof. Dr. Jun Terao Prof. Dr. Yasushi Tsuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7125-7132
The highly selective copper‐catalyzed hydroboration of allenes has been developed. Allylboranes and alkenylboranes were selectively prepared by the judicious choice of catalytic species (copper hydride and boryl copper). Furthermore, two types of alkenylboranes could be selectively synthesized by the choice of an appropriate ligand. Mechanistic studies confirmed that the protonation of a (Z)‐σ‐allyl copper species, which was isolated and structurally characterized by single‐crystal X‐ray diffraction, was a key step in these reactions. Besides allenes, this method is also applicable to the selective hydroboration of 1,3‐diene derivatives to afford allylboranes and homoallylboranes. 相似文献
997.
Hui‐Jun Yun Yun‐Ji Lee Seung‐Jin Yoo Prof. Dae Sung Chung Prof. Yun‐Hi Kim Prof. Soon‐Ki Kwon 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):13242-13248
We describe herein the synthesis of novel donor–acceptor conjugated polymers with dithienobenzodithiophenes (DTBDT) as the electron donor and 2,1,3‐benzothiadiazole as the electron acceptor for high‐performance organic photovoltaics (OPVs). We studied the effects of strategically inserting thiophene into the DTBDT as a substituent on the skeletal structure on the opto‐electronic performances of fabricated devices. From UV/Vis absorption, electrochemical, and field‐effect transistor analyses, we found that the thiophene‐containing DTBDT derivative can substantially increase the orbital overlap area between adjacent conjugated chains and thus dramatically enhance charge‐carrier mobility up to 0.55 cm2 V?1 s?1. The outstanding charge‐transport characteristics of this polymer allowed the realization of high‐performance organic solar cells with a power conversion efficiency (PCE) of 5.1 %. Detailed studies on the morphological factors that enable the maximum PCE of the polymer solar cells are discussed along with a hole/electron mobility analysis based on the space‐charge‐limited current model. 相似文献
998.
Dr. Jun‐ichi Ito Kohei Fujii Prof. Dr. Hisao Nishiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):601-605
NCN‐pincer Ru‐complexes containing bis(oxazolinyl)phenyl ligands serve as suitable catalysts in the direct conjugate additions of α,β‐unsaturated carbonyl compounds, including ketones, esters, and amides, as well as vinylphosphonates, giving various β‐alkynyl carbonyl and phosphonate compounds. A bis(oxazolinyl)phenyl (phebox)–Ru complex also catalyzes the asymmetric conjugate addition of an alkyne with a β‐substituted, α,β‐unsaturated ketone to produce a chiral β‐alkynyl ketone. 相似文献
999.
1000.
Ross S. Winter Dr. Jun Yan Dr. Christoph Busche Dr. Jennifer S. Mathieson Dr. Alessandro Prescimone Prof. Euan K. Brechin Dr. De‐Liang Long Prof. Leroy Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):2976-2981
Two near isomeric clusters containing a novel {Mn8W4} Keggin cluster within a [W36Mn10Si4O136(OH)4(H2O)8]24? cluster are reported: K10Li14 [W36Si4O136MnII10(OH)4(H2O)8] ( 1 ) and K10Li13.5Mn0.25[W36Si4O136MnII10(OH)4(H2O)8] ( 1′ ). Bulk characterization of the clusters has been carried out by single crystal X‐ray structure analysis, ICP‐MS, TGA, ESI‐MS, CV and SQUID‐magnetometer analysis. X‐ray analysis revealed that 1′ has eight positions within the central Keggin core that were disordered W/Mn whereas 1 contained no such disorder. This subtle difference is due to a differences is how the two clusters assemble and recrystallize from the same mother liquor and represents a new type of isomerism. The rapid recrystallization process was captured via digital microscopy and this uncovered two “intermediate” types of crystal which formed temporarily and provided nucleation sites for the final clusters to assemble. The intermediates were investigated by single crystal X‐ray analysis and revealed to be novel clusters K4Li22[W36Si4Mn7O136(H2O)8]?56 H2O ( 2 ) and Mn2K8Li14[W36Si4Mn7O136(H2O)8]?45 H2O ( 3 ). The intermediate clusters contained different yet related building blocks to the final clusters which allowed for the postulation of a mechanism of assembly. This demonstrates a rare example where the use X‐ray crystallography directly facilitated understanding the means by which a POM assembled. 相似文献