Reductive modification of difluoromethylene moiety in pentafluoropropionyl group

The reductive Mg-promoted defluorinative-silylation of 2,2,3,3,3-pentafluoropropiophenone readily produces the α-trifluoromethyl enol silyl ether, which then react with electrophiles to give a variety of 2-substituted-3,3,3-trifluoropropiophenones in excellent yields. The same protocol is applicable for the preparation of enol silyl ether of 3,3,3-trifluoropropiophenone. Fluoride ion catalyzed 1,2-desilylative-defluorination of 2,3,3,3-tetrafluoro-2-trimethylsilyloxypropiophenone provided 3,3,3-trifluoro-1-phenyl-1,2-propanedione in a good yield.     

Uniform mixing of antiferromagnetism and high-temperature superconductivity in electron-doped layers of four-layered Ba(2)Ca(3)Cu(4)O(8)F(2): a new phenomenon in an electron underdoped regime

We report (63,65)Cu- and (19)F-NMR studies on a four-layered high-temperature superconductor Ba(2)Ca(3)Cu(4)O(8)F(2)((0234F(2.0)) with apical fluorine (F(-1)), an undoped 55 K superconductor with a nominal Cu(2+) valence on average. We reveal that this compound exhibits the antiferromagnetism (AFM) with a Néel temperature T(N)=100 K despite being a T(c)=55 K superconductor. Through a comparison with a related trilayered cuprate Ba(2)Ca(3)Cu(4)O(8)F(2)(0233F(2.0)), it is demonstrated that electrons are transferred from the inner plane (IP) to the outer plane (OP) in 0234F(2.0) and 0223F(2.0), confirming the self-doped high-temperature superconductivity (HTSC) having electron and hole doping in a single compound. Remarkably, uniform mixing of AFM and HTSC takes place in both the electron-doped OPs and the hole-doped IPs in 0234F(2.0).     

Synthesis of Structurally Well‐Defined Telechelic Polymers by Organostibine‐Mediated Living Radical Polymerization: In Situ Generation of Functionalized Chain‐Transfer Agents and Selective ω‐End‐Group Transformations

Several organostibine chain‐transfer agents possessing polar functional groups have been prepared by the reactions of azo initiators and tetramethyldistibine ( 1 ). Carbon‐centered radicals thermally generated from the azo initiators were trapped by 1 to yield the corresponding organostibine chain‐transfer agents. The high yields observed in the synthesis of the chain‐transfer agents strongly suggest that distibines have excellent radicophilic reactivity. As the reactions proceeded under neutral conditions, functional groups that are incompatible with ionic conditions were incorporated into the chain‐transfer agents. The chain‐transfer agents were used in living radical polymerization to synthesize the corresponding α‐functionalized polymers. As the functional groups in the chain‐transfer agents did not interfere with the polymerization reaction, well‐controlled polymers possessing number‐average molecular weights (M_ns) predetermined by the monomer/transfer agent ratios were synthesized with low polydispersity indices (PDIs). The organostibanyl ω‐polymer ends were transformed into a number of different functional groups by radical‐coupling, radical‐addition, and oxidation reactions. Therefore, it was possible to synthesize well‐controlled telechelic polymers with the same and also with different functional groups at their α‐ and ω‐polymer ends. Distibine 1 was also found to increase PDI control in the living radical polymerization of styrene and methyl methacrylate (MMA) using a purified organostibine chain‐transfer agent. Well‐controlled poly(methyl methacrylate)s with M_n values ranging from 10 000 to 120 000 with low PDIs (1.05–1.15) were synthesized by the addition of a catalytic amount of 1 . The results have been attributed to the high reactivity of distibine 1 towards polymer‐end radicals, which are spontaneously deactivated to yield organostibine dormant species.     

Electronic states near fermi level in superconductors La2 − x Sr x CuO4 by means of x-ray absorption spectra near Cu-K and La-L edges

The electronic states of La_{2? x} Sr _x CuO₄ with 0.00 ≤ x ≤ 0.20 are studied by means of X-ray absorption spectroscopy (XANES, EXAFS) near the K-edge of Cu²⁺ ion and the L-edges of La³⁺ ion. It is found that characteristic white lines occurring near L _II and L _III edges of La³⁺ ion show a slight energy shift depending on substituted Sr²⁺ ions, x and temperature. The white lines suggest that unoccupied high-density 5dπ and 5dδ bands of La³⁺ ion just above a Fermi level transform to a hybridized single band of 5dπδ at 78?K in the superconductors with x = 0.10, 0.16 and 0.20. On the other hand, the XANES spectra near the Cu-K edge including a pre-edge region do not depend on x and temperature in the region of 0.00 ≤ x ≤ 0.20. It is considered that there is no reconstruction of electronic states at the Fermi level in a Mott–Hubbard band gap between an O 2p valence band and a Cu 3d conduction band. The electronic states at the Fermi level are probably consisted of the unoccupied 5dπδ band and an empty charge-transfer 3d?⁹ L band at low temperature, bands of which occur in a band gap between a filled O 2p valence band and an unoccupied O 2p conduction band. The insulator–superconductor–metal transitions in La_{2? x} Sr _x CuO₄ are related to the 5dπδ and 3d?⁹ L bands and holes, which site at a top region of the O 2p valence band near the Fermi level produced by a substitution of La³⁺ with Sr²⁺ ions.     

Uniform mixing of high-Tc superconductivity and antiferromagnetism on a single CuO2 plane of a Hg-based five-layered cuprate

We report a site selective Cu-NMR study on underdoped Hg-based five-layered high-Tc cuprate HgBa2Ca4CU5O(12+delta) with a Tc = 72 K. Antiferromagnetism (AFM) has been found to take place at T(N) = 290 K, exhibiting a large antiferromagnetic moment of 0.67-0.69 microB at three inner planes (IP). This value is comparable to the values reported for nondoped cuprates, suggesting that the IP may be in a nearly nondoped regime. Most surprisingly, the AFM order is also detected with M(AFM)(OP) = 0.1 microB even at two outer planes (OP) that are responsible for the onset of superconductivity (SC). The high-Tc SC at Tc = 72 K can uniformly coexist on a microscopic level with the AFM at OP's. This is the first microscopic evidence for the uniform mixed phase of AFM and SC on a single CuO2 plane in a simple environment without any vortex lattice and/or stripe order.     

High-pressure synthesis and crystal structure analysis of NaMn2O4 with the calcium ferrite-type structure

Single crystals of a new sodium manganese oxide, NaMn₂O₄, were synthesized for the first time using a high-temperature and high-pressure technique. The NaMn₂O₄ single crystal is black, has a needle shape, and crystallizes in the orthorhombic calcium ferrite-type structure, space group Pnam with , , , , and Z=4. The structure was determined from a single-crystal X-ray study and refined to the conventional values R=0.041 and wR=0.034 for 1190 observed reflections. The framework structure is built up from edge-sharing chains of MnO₆ octahedra that condense to form one-dimensional tunnels in which the sodium atoms are located. The Mn-O bond distance and bond valence analyses revealed the manganese valence Mn³⁺/Mn⁴⁺ ordering in the two “double rutile” chains of NaMn₂O₄.     

Wandering in color-space why is the life of pentaquark so long?

The problem of the long life time of the pentaquark Θ⁺ is investigated on the basis of the color molecular dynamics simulation. We find that it takes a long time (typically of 50–100 fm/c) for the initial pentaquark state to rearrange its color and spatial positions to decay into the nucleon+kaon final state. Structure of the potential surface in the color and position spaces also supports this picture. Pentaquark wanders on the potential surface to find a narrow channel to decay.