An unusual phase transition to a second liquid vortex phase in the superconductor YBa2Cu3O7

A magnetic field penetrates a superconductor through an array of 'vortices', each of which carries one quantum of flux that is surrounded by a circulating supercurrent. In this vortex state, the resistivity is determined by the dynamical properties of the vortex 'matter'. For the high-temperature copper oxide superconductors (see ref.1 for a theoretical review), the vortex phase can be a 'solid', in which the vortices are pinned, but the solid can 'melt' into a 'liquid' phase, in which their mobility gives rise to a finite resistance. (This melting phenomenon is also believed to occur in conventional superconductors, but in an experimentally inaccessible part of the phase diagram.) For the case of YBa2Cu3O7, there are indications of the existence of a critical point, at which the character of the melting changes. But neither the thermodynamic nature of the melting, nor the phase diagram in the vicinity of the critical point, has been well established. Here we report measurements of specific heat and magnetization that determine the phase diagram in this material to 26 T, well above the critical point. Our results reveal the presence of a reversible second-order transition above the critical point. An unusual feature of this transition-namely, that the high-temperature phase is the less symmetric in the sense of the Landau theory-is in accord with theoretical predictions of a transition to a second vortex-liquid phase.     

A tri-coordinate hydrogen ligand in a trinuclear iridium cluster

The novel complex [{IrH₂,(PCy₃)(C₅H₅N)}₃(μ₃-H)] [PF₆]₂ has been characterized by X-ray crystallography, IR and ¹H NMR spectroscopy. It contains a tricoordinate hydrogen ligand within a triangle of iridium atoms.     

A rare eta2-butadienyl complex from an alkyne double insertion with double vinylidene rearrangement

A rare eta2-butadienyl Ir(III) complex with a weak Ir...C bond is formed from 1-alkyne double insertion with the independent double alkyne to vinylidene rearrangement. A reaction intermediate is isolated, and labeling and crossover experiments indicate the intramolecularity of both alkyne to vinylidene rearrangements.     

An Accurate Molecular Structure of Phenyl,the Simplest Aryl Radical

The phenyl radical (C₆H₅^.) is the prototypical σ‐type aryl radical and one of the most common aromatic building blocks for larger ring molecules. Using a combination of rotational spectroscopy of singly substituted isotopic species and vibrational corrections calculated theoretically, an extremely accurate molecular structure has been determined. Relative to benzene, the phenyl radical has a substantially larger C‐C_ipso‐C bond angle [125.8(3)° vs. 120°], and a shorter distance [2.713(3) Å vs. 2.783(2) Å] between the ipso and para carbon atoms.     

An Accurate Molecular Structure of Phenyl,the Simplest Aryl Radical

The phenyl radical (C₆H₅^.) is the prototypical σ‐type aryl radical and one of the most common aromatic building blocks for larger ring molecules. Using a combination of rotational spectroscopy of singly substituted isotopic species and vibrational corrections calculated theoretically, an extremely accurate molecular structure has been determined. Relative to benzene, the phenyl radical has a substantially larger C‐C_ipso‐C bond angle [125.8(3)° vs. 120°], and a shorter distance [2.713(3) Å vs. 2.783(2) Å] between the ipso and para carbon atoms.     

Distinct mechanisms of bridging-oxo exchange in di-mu-O dimanganese complexes with and without water-binding sites: implications for water binding in the O(2)-evolving complex of photosystem II

Isotopic exchange between oxygens of water and mu-O bridges in the di-mu-O dimanganese complexes, [(mes-terpy)2Mn2(III/IV)(mu-O)2(H2O)2](NO3)3 (1, mes-terpy = 4'-mesityl-2,2':6',2' '-terpyridine) and [(phen)4Mn2III/IV(mu-O)2](ClO4)3 (2, phen = 1,10-phenanthroline), has been investigated by a study of the kinetics of exchange. The data provide evidence for distinct mechanisms of exchange in 1 and 2 and suggest that these differences arise due to the presence and absence of terminal water-binding sites in 1 and 2, respectively. Exchange of oxygen atoms between water and mu-O bridges must involve the elementary steps of bridge protonation, deprotonation, opening, and closing. On the basis of the existing literature on these reactions in oxo-bridged metal complexes and our present data, we propose pathways of exchange in 1 and 2. The mechanism proposed for 1 involves an initial fast protonation of an oxo-bridge by water coordinated to Mn(IV), followed by a slow opening of the protonated bridge as proposed earlier for an analogous complex on the basis of DFT calculations. The mechanism proposed for 2 involves initial dissociation of phen, followed by coordination of water at the vacated sites, as observed for rearrangement of 2 to a trinuclear complex. The subsequent steps are proposed to be analogous to those for 1. Our results are discussed in the context of data on 18O-labeled water isotope exchange in photosystem II and provide support for the existence of fully protonated terminal waters bound to Mn in the O2-evolving complex of photosystem II.     

Mild, Reversible Reaction of Iridium(III) Amido Complexes with Carbon Dioxide

Unlike some other Ir(III) hydrides, the aminopyridine complex [(2-NH(2)-C(5)NH(4))IrH(3)(PPh(3))(2)] (1-PPh(3)) does not insert CO(2) into the Ir-H bond. Instead 1-PPh(3) loses H(2) to form the cyclometalated species [(κ(2)-N,N-2-NH-C(5)NH(4))IrH(2)(PPh(3))(2)] (2-PPh(3)), which subsequently reacts with CO(2) to form the carbamato species [(κ(2)-O,N-2-OC(O)NH-C(5)NH(4))IrH(2)(PPh(3))(2)] (10-PPh(3)). To study the insertion of CO(2) into the Ir-N bond of the cyclometalated species, a family of compounds of the type [(κ(2)-N,N-2-NR-C(5)NH(4))IrH(2)(PR'(3))(2)] (R = H, R' = Ph (2-PPh(3)); R = H, R' = Cy (2-PCy(3)); R = Me, R' = Ph (4-PPh(3)); R = Ph, R' = Ph (5-PPh(3)); R = Ph, R' = Cy (5-PCy(3))) and the pyrimidine complex [(κ(2)-N,N-2-NH-C(4)N(2)H(3))IrH(2)(PPh(3))(2)] (6-PPh(3)) were prepared. The rate of CO(2) insertion is faster for the more nucleophilic amides. DFT studies suggest that the mechanism of insertion involves initial nucleophilic attack of the nitrogen lone pair of the amide on CO(2) to form an N-bound carbamato complex, followed by rearrangement to the O-bound species. CO(2) insertion into 1-PPh(3) is reversible in the presence of H(2) and treatment of 10-PPh(3) with H(2) regenerates 1-PPh(3), along with Ir(PPh(3))(2)H(5).