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71.
Quarez E Hsu KF Pcionek R Frangis N Polychroniadis EK Kanatzidis MG 《Journal of the American Chemical Society》2005,127(25):9177-9190
The nature of the thermoelectric materials Ag(1-x)Pb(m)SbTe(m+2) or LAST-m materials (LAST for Lead Antimony Silver Tellurium) with different m values at the atomic as well as nanoscale was studied with powder/single-crystal X-ray diffraction, electron diffraction, and high-resolution transmission electron microscopy. Powder diffraction patterns of different members (m = 0, 6, 12, 18, infinity) are consistent with pure phases crystallizing in the NaCl-structure-type (Fmm) and the proposition that the LAST family behaved as solid solutions between the PbTe and AgSbTe2 compounds. However, electron diffraction and high resolution transmission electron microscopy studies suggest the LAST phases are inhomogeneous at the nanoscale with at least two coexisting sets of well-defined phases. The minority phase which is richer in Ag and Sb is on the nanosized length scale, and it is endotaxially embedded in the majority phase which is poorer in Ag and Sb. Moreover, within each nanodomain we observe extensive long range ordering of Ag, Pb, and Sb atoms. The long range ordering can be confirmed by single crystal X-ray diffraction studies. Indeed, data collections of five different single crystals were successfully refined in space groups of lower symmetry than Fmm including P4/mmm and Rm. The results reported here provide experimental evidence for a conceptual basis that could be employed when designing high performance thermoelectric materials and dispel the decades long belief that the systems (AgSbTe2)(1-x)(PbTe)x are solid solutions. 相似文献
72.
Alexandra M. Antonio Kyle J. Korman Glenn P. A. Yap Eric D. Bloch 《Chemical science》2020,11(46):12540
Diverse strategies for the preparation of mixed-metal three-dimensional porous solids abound, although many of them lend themselves only moderate levels of tunability. Herein, we report the design and synthesis of surface functionalized permanently microporous coordination cages and their use in the isolation of mixed metal solids. Judicious alkoxide-based ligand functionalization was utilized to tune the solubility of starting copper(ii)-based cages and their resulting compatibility with the mixed-cage approach described here. We further prepared a family of isostructural molybdenum(ii) cages for a subset of the ligands. The preparation of mixed-metal cage solids proceeds under facile conditions where solutions of parent cages are mixed and product phases isolated. A suite of spectroscopic and characterization tools confirm the starting cages are intact in the amorphous product. Finally, we show that utilization of precise ligand functional groups can be used to prepare mixed cage solids that can be easily and cleanly separated into their constituent components through simple solvent washing or solvent extraction techniques.Surface-functionalized porous coordination cages can be used to create homogeneous mixed-cage alloys with high levels of tunability and processability. 相似文献
73.
Burford N Ragogna PJ McDonald R Ferguson MJ 《Chemical communications (Cambridge, England)》2003,(16):2066-2067
Polyphosphorus dications have been synthesised and comprehensively characterised as diphosphine (dppe, dmpe and dpph) linked Ar2P+ Lewis acids (Ar = C6H5); this application of unique homoatomic coordination chemistry provides important building blocks for extended systems. 相似文献
74.
Neil G. Connelly John G. Crossley A. Guy Orpen Henrietta Salter 《Journal of organometallic chemistry》1994,480(1-2):c12-c13
The reaction of [NBu4n]2Cu(mnt)2] with [Pt(CNMe)4][PF6]2 gives [Pt(mnt)(CNMe)2]·(NC)2C2S2CNMe, an X-ray study of which reveals co-stacking of neutral planar metal and organic molecules. 相似文献
75.
Gaballah ST Hussein YH Anderson N Lian TT Netzel TL 《The journal of physical chemistry. A》2005,109(48):10832-10845
Femtosecond, picosecond, and nanosecond transient absorbance (TA) and picosecond emission kinetics results are presented for three 5-(1-pyrenyl)-2'-deoxyuridine nucleosides each with a different two-atom linker joining pyrenyl C-1 to uracil C-5. The linkers are respectively -NHCO-, -(CH(2))(2)-, and -C[triple bond]C- for PAdU, PEdU, and PYdU. For all three nucleoside conjugates, most conformers undergo intramolecular charge transfer (CT) from their pyrenyl (1)(pi,pi) excited states to form Py(*+)/dU(*-) CT products in ultrashort times: 相似文献
76.
Zijp EJ van der Vlugt JI Tooke DM Spek AL Vogt D 《Dalton transactions (Cambridge, England : 2003)》2005,(3):512-517
Chiral aminophosphines Ph2PN(R)(CH2)nN(R)PPh2 1-4 [n= 2, R = CH(CH3)(Ph) 1; n= 3, R = CH(CH2CH3)(Ph) 2, n= 2, R = CH(CH3)(1-naphthyl) 3; n= 2, R = CH(CH3)(C6H11) 4] were synthesized by the reaction of ClPPh2 with the appropriate easily accessible enantiopure amine building blocks. For compounds 1 and 2, the corresponding selenides 5 and 6 were prepared to determine the electronic character of the phosphine moieties. By reaction of 1 with either PdCl2(cod) or PdCl(CH3)(cod) the cis-complexes 7 and 8 were obtained. The molecular structure for complex 7, cis-[PdCl2(1)], was determined by X-ray crystallography. Reaction of PtCl2(cod) with 1 or 2 yielded the corresponding monomeric cis-isomers 9 and 10. The rhodium derivative [RhCl(CO)(1)] (11) was obtained as a mixture of cis and trans-isomers. Preliminary results in the rhodium catalyzed hydroformylation of styrene and vinyl acetate, with ee's up to 51% and high regioselectivities, showed the potential of these chiral aminophosphines for homogeneous catalysis. 相似文献
77.
Burford N Cameron TS Clyburne JA Eichele K Robertson KN Sereda S Wasylishen RE Whitla WA 《Inorganic chemistry》1996,35(19):5460-5467
The phosphadiazonium cation [MesNP](+) reacts quantitatively with the fluorenylide anion, MesNH(2), and MesOH (Mes = 2,4,6-tri-tert-butylphenyl), resulting in formal insertion of the N-P moiety into the H-Y (Y = C, N, O) bonds. Specifically, reaction of MesNPCl with fluorenyllithium gives the aminofluorenylidenephosphine [crystal data: C(31)H(38)NP, monoclinic, P2(1)/c, a = 9.568(8) ?, b = 24.25(2) ?, c = 11.77(1) ?, beta = 101.38(8) degrees, Z = 4]. Similarly, reaction of [MesNP][GaCl(4)] with MesNH(2) gives the diaminophosphenium salt [MesN(H)PN(H)Mes][GaCl(4)] [crystal data: C(36)H(60)Cl(4)GaN(2)P, monoclinic, C2/c, a = 24.921(2) ?, b = 10.198(4) ?, c = 16.445(2) ?, beta = 93.32(1) degrees, Z = 4], and reaction with MesOH gives the first example of an aminooxyphosphenium salt [MesN(H)POMes][GaCl(4)]. It is proposed that the reactions involve nucleophilic attack at phosphorus followed by a 1,3-hydrogen migration from Y to N. Experimental evidence for the formation of sigma-complex intermediates is provided by the isolation of [MesNP-PPh(3)][SO(3)CF(3)] [crystal data: C(37)H(44)F(3)NO(3)P(2)S, triclinic, P&onemacr;, a = 10.663(1) ?, b = 19.439(1) ?, c = 10.502(1) ?, alpha = 103.100(7) degrees, beta = 113.311(7) degrees, gamma = 93.401(7) degrees, Z = 2]. As part of the unequivocal characterization of the aminooxyphosphenium salt, detailed solid-state (31)P NMR studies and GIAO calculations on the phosphenium cations have been performed. Contrary to popular belief, the phosphorus shielding in dicoordinate cations is not caused by the positive charge but results from efficient mixing between the phosphorus lone pair and pi orbitals. 相似文献
78.
[reaction: see text] Treatment of 1,4-dilithio-1,3-butadiyne (1) with dichalcogenides RSSR or RSeSeR affords dithio- and diseleno-1,3-butadiynes (2, 3), perthio- and perseleno-[3]-cumulenes (4, 5), perthio- and perseleno-1,3-butadienes (6, 7), and/or perthio- and perseleno-but-1-ene-3-ynes (8, 9). The products can be controlled by stoichiometry and temperature, by the presence or absence of oxygen, and by choice of the "R" group. By X-ray crystallography, hexa(methylthio)-1,3-butadiene is highly twisted, with a torsion angle [Phi(CCCC)] of 84.7 degrees and an elongated C(2)-C(3) distance of 1.484(3) A. 相似文献
79.
Total synthesis of amaryllidaceae alkaloid buflavine 总被引:1,自引:0,他引:1
A concise synthesis of the amaryllidaceae alkaloid buflavine (1) and its regioisomer (2) involving sequential Meyers' biaryl coupling, enecarbamate formation, and hydrogenation followed by ultimate intramolecular reductive amination is presented. 相似文献
80.
Effect of Enzyme Modification of Corn Grits on their Properties as an Adsorbent in a Skarstrom Pressure Swing Cycle Dryer 总被引:1,自引:0,他引:1
Corn grits have been tested as a desiccant in a pressure swing adsorption (PSA) system to produce dry air. Two sizes of unmodified corn grits were tested in the PSA system: 2.16 and 0.978 mm in diameter, which dried moist air to dew points of –42°C and –69°C, respectively. A modification technology has been developed for the corn grits that gives an increase in the operational adsorptive capacity in a pressure swing adsorption system, so that they remove as much moisture from air as molecular sieves at the same conditions. After modification, 2.16 mm corn grits dry moist air to a –56°C dew point and the 0.978 mm corn grits dry air to a –80°C dew point. The modification process creates surface modifications on the corn grits apparently making more adsorption sites easily available. The modification procedure increases the specific surface area of the grits and possibly decreases the crystallinity, which would make more hydroxyl groups available for adsorption of water. Possible applications of using corn grits in the pressure swing adsorption system include industrial gas dryers, sorptive cooling air conditioners, and recycling equipment for industrial solvents. 相似文献