Syntheses of Cationic, Six-Coordinate Cadmium(II) Complexes Containing Tris(pyrazolyl)methane Ligands. Influence of Charge on Cadmium-113 NMR Chemical Shifts

Treating a thf (thf = tetrahydrofuran) suspension of Cd(acac)(2) (acac = acetylacetonate) with 2 equiv of HBF(4).Et(2)O results in the immediate formation of [Cd(2)(thf)(5)](BF(4))(4) (1). Crystallization of this complex from thf/CH(2)Cl(2) yields [Cd(thf)(4)](BF(4))(2) (2), a complex characterized in the solid state by X-ray crystallography. Crystal data: monoclinic, P2(1)/n, a = 7.784(2) ?, b = 10.408(2) ?, c = 14.632(7) ?, beta = 94.64(3) degrees, V = 1181.5(6) ?(3), Z = 2, R = 0.0484. The geometry about the cadmium is octahedral with a square planar arrangement of the thf ligands and a fluorine from each (BF(4))(-) occupying the remaining two octahedral sites. Reactions of [Cd(2)(thf)(5)](BF(4))(4) with either HC(3,5-Me(2)pz)(3) or HC(3-Phpz)(3) yield the dicationic, homoleptic compounds {[HC(3,5-Me(2)pz)(3)](2)Cd}(BF(4))(2) (3) and {[HC(3-Phpz)(3)](2)Cd}(BF(4))(2) (4) (pz = 1-pyrazolyl). The solid state structure of 3 has been determined by X-ray crystallography. Crystal data: rhombohedral, R&thremacr;, a = 12.236(8) ?, c = 22.69(3) ?, V = 2924(4) ?(3), Z = 3, R = 0.0548. The cadmium is bonded to the six nitrogen donor atoms in a trigonally distorted octahedral arrangement. Four monocationic, mixed ligand tris(pyrazolyl)methane-tris(pyrazolyl)borate complexes {[HC(3,5-Me(2)pz)(3)][HB(3,5-Me(2)pz)(3)]Cd}(BF(4)) (5), {[HC(3,5-Me(2)pz)(3)][HB(3-Phpz)(3)]Cd}(BF(4)) (6), {[HC(3-Phpz)(3)][HB(3,5-Me(2)pz)(3)]Cd}(BF(4)) (7), and {[HC(3-Phpz)(3)][HB(3-Phpz)(3)]Cd}(BF(4)) (8) are prepared by appropriate conproportionation reactions of 3or 4 with equimolar amounts of the appropriate homoleptic neutral tris(pyrazolyl)borate complexes [HB(3,5-Me(2)pz)(3)](2)Cd or [HB(3-Phpz)(3)](2)Cd. Solution (113)Cd NMR studies on complexes 3-8 demonstrate that the chemical shifts of the new cationic, tris(pyrazolyl)methane complexes are very similar to the neutral tris(pyrazolyl)borate complexes that contain similar substitution of the pyrazolyl rings.     

Probing chemical transformations in organic solids via NMR techniques: The solid-state photodimerization reaction of 7-methoxy-4-methylcoumarin

It has been reported that crystalline 7-methoxy-4-methylcoumarin undergoes a [2 + 2] photodimerization reaction to give two different products; the major product is thesyn head-head dimer, whereas the minor product is thesyn head-tail dimer. In this paper, high-resolution solid-state¹³C NMR and solution-state¹H and¹³C NMR techniques have been applied to investigate various structural issues relating to this solid-state photodimerization reaction. In particular, spectra have been recorded at various stages during the progress of the photodimerization reaction with the aim of charting the structural changes in the system as a function of reaction progress, with particular interest in assessing the potential of this technique for investigating the structural reasons for the production of the minor product. Conformational and dynamic properties of the product obtained in this solid-state photodimerization reaction have also been assessed.     

Dynamics of Bose-Einstein condensates with atomic pumping and dissipative processes

In the dynamics of condensed systems described by a nonconservative non-linear Schrödinger equation, we investigate numerically the role of atomic feeding and inelastic collisions where dipolar relaxation is the dominant process. By analyzing the range of possible values of the nonconservative parameters to have stable (or unstable) solutions, we verify that spatio-temporal chaos patterns, known for attractive two-body systems due to collapsing effects, can also occur in the repulsive case when the term corresponding to the linear atomic feeding dominates the nonconservative contributions.     

Influence of photoperiod and running wheel access on the entrainment of split circadian rhythms in hamsters

Background  

In the laboratory, behavioral and physiological states of nocturnal rodents alternate, with a period near 24 h, between those appropriate for the night (e.g., elevated wheel-running activity and high melatonin secretion) and for the day (e.g., rest and low melatonin secretion). Under appropriate 24 h light:dark:light:dark conditions, however, rodents may be readily induced to express bimodal rest/activity cycles that reflect a global temporal reorganization of the central neural pacemaker in the hypothalamus. We examine here how the relative length of the light and dark phases of the environmental cycle influences this rhythm splitting and the necessity of a running wheel for expression of this entrainment condition.     

Electronic spectra of potassium bromide containing thallium II. Emission spectrum excited at 2537 Å

The emission spectrum of KBr: Tl⁺ excited at 2537 Å has been measured in the temperature range 15–296°K. At low temperatures the spectrum consists of a prominent band at 4.01 eV, a much smaller band at 3.40 eV and a very small band at 3.15 eV. The last does not appear to change much with temperature and so could not be measured accurately. The temperature-dependence of the two main bands is complex. Between 60 and 100°K the low-energy band increases sharply in intensity, while the high-energy band decreases correspondingly. Above 110°K the situation reverses and the low-energy band decreases in intensity while the high-energy band grows. Both bands closely approximate symmetric Gaussians. The temperature-dependence of the intensity of these two bands is well-explained qualitatively by the existence of two kinds of minima on the adiabatic potential energy surface for the A state. However, predictions of the temperature-dependence of the two emission bands based on calculated adiabatic potential energy surfaces are not in quantitative agreement with the experimental results. Possible reasons for this are our lack of knowledge of precise values for the parameters which enter into the theory, namely the spin-orbit coupling constant, the exchange integral, and the electron lattice coupling constant. The possible role of the ³A_1u state in emission is discussed briefly.     

Classical Behavior After a Phase Transition: I. Classical Order Parameters

We analyze the onset of classical field configurations after a phase transition. Firstly, we motivate the problem by means of a toy model in quantum mechanics. Subsequently, we consider a scalar field theory in which the system-field interacts with its environment, represented both by further scalar fields and by its own short-wavelength modes. We show that for very rapid quenches, the order parameter can be treated classically by the time taken for it to achieve its ground state values (spinodal time).     

Relations between a manifold and its focal set

Summary Throughout this paper, smooth meansC . All manifolds and embeddings will be smooth. By aclosed m-manifold we mean a compact connected manifold of dimensionm, without boundary.LetM be a closedm-manifold (m>0), andf: ME ⁿ an embedding in Euclideann-space. The focal points off are the centres of principal curvature (with respect to some normal direction) of the embedded manifoldf(M). These points form thefocal set C(f) off.The starting point for our investigation is the following problem. Is there any relation between the topological structure ofM and the relative positions ofC(f) andf(M) inE ⁿ ? In particular, canf be so chosen thatC(f) andf(M) are disjoint? We say that such an embedding isnonfocal.We find that there are manifolds for which no such embedding exists.     

Quark trapping in the quantised scalar SLAC ‘bag’ model

We build simple ‘bags’ (quarks plus scalars), based on the simplest SLAC Lagrangian, upon the Hartree-Fock vacuum. For relatively weak quark coupling (at least) the self-consistent quantum fluctuations prevent good quark confinement.