Formation of linkage isomers via the substitution of halides by selenocyanate in ruthenium(III) complexes

Summary Substitution of the halide ion of [Ru(NH₃)₅X]²⁺ (X=Cl^– or Br^–) by SeCN^– was monitored spectrophotometrically between 45 and 60° C in aqueous medium. The pseudo-first order rate constants were evaluated by Guggenheim's procedure, which shows linearity for 2–3 half-lives. The rate increases linearly with [SeCN^–] and all the plots have a positive intercept on the rate axis. The SeCN^–-independent path represents aquation and the SeCN^–-dependent path represents anation of the aqua complex with simultaneous formation of two isomeric (the N bonded and the Se bonded) products. The formation of the isomeric products is entropy controlled.     

Magnetostructural studies on ferromagnetically coupled copper(II) cubanes of Schiff-base ligands

Three cubane copper(II) clusters, namely [Cu(4)(HL')4] (1), [Cu4L2(OH)2] (2), and [Cu4L2(OMe)2] (3), of two pentadentate Schiff-base ligands N,N'-(2-hydroxypropane-1,3-diyl)bis(acetylacetoneimine) (H3L') and N,N'-(2-hydroxypropane-1,3-diyl)bis(salicylaldimine) (H3L), are prepared, structurally characterized by X-ray crystallography, and their variable-temperature magnetic properties studied. Complex 1 has a metal-to-ligand stoichiometry of 1:1 and it crystallizes in the cubic space group P43n with a structure that consists of a tetranuclear core with metal centers linked by a mu(3)-alkoxo oxygen atom to form a cubic arrangement of the metal and oxygen atoms. Each ligand displays a tridentate binding mode which means that a total of eight pendant binding sites remain per cubane molecule. Complexes [Cu4L2(OH)2] (2) and [Cu4L2(OMe)2] (3) crystallize in the orthorhombic space group Pccn and have a cubane structure that is formed by the self-assembly of two {Cu2L}+ units. The variable-temperature magnetic susceptibility data in the range 300-18 K show ferromagnetic exchange interactions in the complexes. Along with the ferromagnetic exchange pathway, there is also a weak antiferromagnetic exchange between the copper centers. The theoretical fitting of the magnetic data gives the following parameters: J1 = 38.5 and J2 = -18 cm(-1) for 1 with a triplet (S = 1) ground state and quintet (S = 2) lowest excited state; J1 = 14.7 and J2 = -18.4 cm(-1) for 2 with a triplet ground state and singlet (S = 0) lowest excited state; and J1 = 33.3 and J2 = -15.6 cm(-1) for 3 with a triplet ground state and quintet lowest excited state, where J1 and J2 are two different exchange pathways in the cubane {Cu4O4} core. The crystal structures of 2 * 6 H2O and 3 * 2 H2O * THF show the presence of channels containing the lattice solvent molecules.     

Synthesis and Structures of New Oxidation/ Cycloaddition Products of λ3‐Cyclodiphosphazanes

Reaction of the cyclodiphosphazane [(OC₄H₈N)P(μ‐N‐t‐Bu)₂P(HN‐t‐Bu)] ( 1 ) with an equimolar quantity of diisopropyl azodicarboxylate afforded the phosphinimine product [(OC₄H₈N)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂ ‐i‐Pr)NHCO₂‐i‐Pr] ( 6 ) having a P^III‐N‐P^V skeleton. Similar products [(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂Et)NHCO₂Et] ( 7 ) and [(CO₂‐i‐Pr)HNN(CO₂‐i‐Pr)](t‐BuN=P(μ‐N‐t‐Bu)₂POCH₂CMe₂CH₂O[P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂‐i‐Pr)NH(CO₂‐i‐Pr)] ( 8 ) were spectroscopically characterized in the reaction of [(t‐BuNH)P‐N‐t‐Bu]₂ ( 2 ) and [(t‐BuNH)P(μ‐N‐t‐Bu)₂POCH₂CMe₂CH₂OP(μ‐N‐t‐Bu)₂P(NH‐t‐Bu)] ( 3 ) with diethyl‐ and diisopropyl azodicarboxylate, respectively. By contrast, the reaction of [(μ‐t‐BuN)P]₂[O‐6‐t‐Bu‐4‐Me‐C₆H₂]₂CH₂ ( 4 ) and [(C₅H₁₀N)P‐μ‐N‐t‐Bu]₂ ( 5 ) with diisopropyl azodicarboxylate afforded the mono‐ and bis‐oxidized compounds [(O)P(μ‐N‐t‐Bu)₂P][O‐6‐t‐Bu‐4‐Me‐C₆H₂]₂CH₂ ( 9 ) and [(C₅H₁₀N)(O)P‐μ‐N‐t‐Bu]₂ ( 10 ), respectively. Oxidative addition of o‐chloranil to 7 and its DIAD analogue [(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂‐i‐Pr)NHCO₂‐i‐Pr] ( 11 ) afforded [(C₆Cl₄‐1, 2‐O₂)(t‐BuNH)P(μ‐N‐t‐Bu)₂P=N‐t‐Bu)(N(CO₂R)NHCO₂R] [R = Et ( 12 ) and i‐Pr ( 13 )] containing tetra‐ and pentacoordinate P^V atoms in the cyclodiphosphazane ring. The structures of 6 , 9 , 12 and 13 have been confirmed by X‐ray structure determination. For comparison, the X‐ray structure of the double cycloaddition product [(C₆Cl₄‐1, 2‐O₂)(t‐BuNH)PN‐t‐Bu]₂ ( 14 ), obtained from the reaction of 2 with two mole equivalents of o‐chloranil is also reported.     

Broken time-reversal symmetry in strongly correlated ladder structures

We provide, for the first time, in a doped strongly correlated system (two-leg ladder), a controlled theoretical demonstration of the existence of a state in which long-range ordered orbital currents are arranged in a staggered pattern, coexisting with a charge density wave. The method used is the highly accurate density-matrix renormalization group technique. This brings us closer to recent proposals that this order is realized in the enigmatic pseudogap phase of the cuprate high temperature superconductors.     

Ion detection with photonic crystal microcavities

We have experimentally demonstrated a cation and anion sensor by using short linear photonic crystal microcavities with an embedded quantum dot active region. The photonic crystal microcavity covered with an ion-selective polymer forms a submicrometer optical detection system sensitive to small changes of perchlorate anion (ClO4(-)) and calcium cation (Ca2+) concentrations.     

The disappearance of equatorial E s and the reversal of electrojet current

Based on simultaneous observations of the horizontal geomagnetic field component H, sporadic E (E _s ) and E-W electron drifts at stations close to the dip equator within the equatorial electrojet region, it has been found that on quiet days and sometimes on disturbed days, when there is an abnormal large decrease in H during daytime, there is a simultaneous disappearance of E _s and a reversal of the direction of drift of electrons from westward to eastward. This suggests that the disappearance of equatorial E _s during day-time is due to a temporary reversal of the electrojet current, which is caused by the imposition of an additional electrostatic field opposite in direction to that of normal S _a field.     

Study of theS-matrix near bound states in the continuum

The behaviour ofS-matrix for potentials generating bound states in continuum in the neighbourhood of the positive bound state energies is studied. It is shown that unlike the case of usual negative energy bound states, theS-matrix does not have a pole at the positive bound state energy but becomes unity at the energy corresponding to bound states in continuum. Calculations ofS-waveS-matrix for a local potential constructed by Stillinger and Herrick and a separable nonlocal potential constructed by the present authors verify these results. Our results indicate that the bound states embedded in continuum constructedvia the von Neumann and Wigner procedure cannot be interpreted as resonances with zero width.     

Sharp signature of a dx2-y2 quantum critical point in the Hall coefficient of cuprate superconductors

We study the behavior of the Hall coefficient, R(H), in a system exhibiting dx(2)(-y(2)) density-wave order in a regime in which the carrier concentration, x, is tuned to approach a quantum critical point at which the order is destroyed. At the mean-field level, we find that n(Hall)=1/R(H) evinces a sharp signature of the transition. There is a kink in n(Hall) at the critical value of the carrier concentration, x(c); as the critical point is approached from the ordered side, the slope of n(Hall) diverges. Hall transport experiments in the cuprates, at high magnetic fields sufficient to destroy superconductivity, should reveal this effect.