Study of the peak effect phenomenon in single crystals of 2H-NbSe2

The weakly pinned single crystals of the hexagonal 2H-NbSe₂ compound have emerged as prototypes for determining and characterizing the phase boundaries of the possible order-disorder transformations in the vortex matter. We present here a status report based on the ac and dc magnetization measurements of the peak effect phenomenon in three crystals of 2H-NbSe₂, in which the critical current densities vary over two orders of magnitude. We sketch the generic vortex phase diagram of a weakly pinned superconductor, which also utilizes theoretical proposals. We also establish the connection between the metastability effects and pinning.     

Reactions of Ru3(CO)12 with Diphosphenes — A New Route to 50‐Electron Ru3P2 nido‐Clusters

The reaction of the symmetric diphosphene 2, 4, 6‐(CF₃)₃‐C₆H₂‐P=P‐C₆H₂‐2, 4, 6‐(CF₃)₃ 4 with Ru₃(CO)₁₂ led to the 50‐electron Ru₃P₂ nido‐cluster Ru₃(CO)₉[μ‐P‐C₆H₂‐2, 4, 6‐(CF₃)₃]₂ 5 , which in solution at room temperature displays hindered rotation of the aromatic rings about the C(aryl)—P bonds. The structure of 5 was determined by X‐ray crystal structure analysis; its Ru₃P₂ centre forms a distorted square pyramid with one ruthenium atom at the apex. One of the two C₆H₂(CF₃)₃ groups is also appreciably distorted. Temperature‐dependent ¹⁹F NMR studies of the [A₃M₃X]₂ spin system (A = M = CF₃, X = ³¹P) of 5 indicated a rotational barrier ΔG^≠ of 82.3 kJ mol^‐1 at 141 °C. The same Ru₃P₂ core was obtained by the reaction of the unsymmetric diphosphene Mes*‐P=P‐Mes 11 with Ru₃(CO)₁₂; hindered rotation about the C(aryl)—P bonds was also observed, in this case.     

Shaping Solid-State Supramolecular Cavities: Chemically Induced Accordionlike Movement of gamma-Zirconium Phosphate Containing Polyethylenoxide Pillars

The hydrophilic oxygen atoms of polyethylenoxide chains inserted as pillars in gamma-zirconium phosphate form hydrogen bonds with the acid groups of the host. As a result the pillars are almost perpendicular to the gamma layers. Upon changing the pH level of the supernatant solution the hydrogen bonds are broken and the pillars become almost perpendicular to the layers (shown schematically). Thus there is a reversible enlargement-shortening of the interlayer space.     

f-Element disiloxanediolates: novel Si-O-based inorganic heterocycles

The preparation and structural characterization of scandium and f-element complexes derived from the disiloxanediolate dianion, [(Ph2SiO)2O]2-, are reported. Reactions of in situ prepared Ln[N(SiMe3)2]3 (Ln = Eu, Sm, Gd) with (Ph2SiOH)2O in different stoichiometries afforded the lanthanide disiloxanediolates [Eu[[(Ph2SiO)2O]Li(Et2O)]3] (1), [[[(Ph2SiO)2O]Li(dme)]2SmCl(dme)] (2), and [[[((Ph2SiO)2O]Li(thf)2]2GdN(SiMe3)2] (3). In situ formed (Ph2SiOLi)2O reacted with anhydrous NdBr3 (molar ratio 3:1) to give polymeric [[Nd[(Ph2SiO)2O]3[mu-Li(thf)]2[mu2LiBrLi(thf)(Et2O)]]n] (4). Treatment of 3 with Ph2Si(OH)2 in the presence of acetonitrile yielded the dilithium trisiloxanediolate derivative [[Ph2Si(OSiPh2O)2][Li(MeCN)]2]2 (5), which according to an X-ray analysis displays an Li4O4 heterocubane structure. The trinuclear scandium complex [[[(Ph2SiO)2O]Sc(acac)2]2Sc(acac)] (6) was obtained by reaction of [(C5Me5)Sc(acac)2] (C5Me5 = eta5-pentamethylcyclopentadienyl) with (Ph2SiOH)2O in a 3:2 molar ratio. Selective formation of the colorless uranium(VI) derivative [U[Ph2Si(OSiPh20)2]2[(Ph2SiO)2O]] (7) was observed when uranocene, U(eta8-C8H8)2, was allowed to react with (Ph2SiOH)2O. An X-ray diffraction study of the solvated derivative [U[Ph2Si(OSiPh2O)2]2[(Ph2SiO)2O]].Et2O.TMEDA (TMEDA= N,N,N',N'-tetramethyl-ethylenediamine) (7a) revealed the presence of both the original [(Ph2SiO)2O]2- dianion as well as the ring-enlarged [Ph2Si(OSiPh2O)2]2- ligand in the same molecule.     

Coordination Chemistry of Acrylamide: 1. Cobalt(II) Chloride Complexes with Acrylamide – Synthesis and Crystal Structures

The molecular structures of blue dichloro‐tetrakis(acrylamide) cobalt(II), [Co{O‐OC(NH₂)CH=CH₂}₄Cl₂] ( 1 ) and pink hexakis(acrylamide)cobalt(II) tetrachlorocobaltate(II), [Co{O‐OC‐(NH₂)CH=CH₂}₆][CoCl₄] ( 2 ), characterized by single X‐ray diffraction, IR spectroscopy and elemental analyses, are described. The coordination of Co^II in 1 involves a tetragonally distorted octahedral structure with four O‐donor atoms of acrylamide in the equatorial positions and two chloride ions in the apical positions. The second complex 2 in ionic form contains Co^II cations surrounded by an octahedral array of O‐coordinated acrylamide ligands, accompanied by a [CoCl₄]^2? anion.