Photophysical properties of 4,4'-di-tert-butyl-2,2'-bipyridine supported 6-membered 2,2'-diphenyl-X platinacycles (X = CH2, NMe, O)

The six-membered platinacycle complex, Pt((t)Bu(2)bpy)(C(6)H(4)OC(6)H(4)) (6) ((t)Bu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) has been prepared from Pt((t)Bu(2)bpy)Cl(2) and 2,2'-dilithio-diphenyl ether. Platinacycle 6 and its analogs with X = CH(2) (4) and NMe (5) exhibit intense solid-state photoluminescence and nearly identical crystal structures. The photophysical properties of 4-6 in the visible range are dominated by mixed metal-ligand-to-ligand charge transfer (MLL'CT) transitions involving high-lying filled mixed metal-ligand orbitals (ML), composed primarily of platinacyclic ring-based d- and π-orbitals, and a low lying vacant π* orbital (L') of the (t)Bu(2)bpy ligand. Lone pair donation from the bridging oxygen atom and especially the NMe group increases the energy of the mixed metal-ligand orbital (ML) without altering the energy of the (t)Bu(2)bpy π* orbital. As a result, the MLL'CT state energy decreases and the absorption and emission wavelengths are red-shifted. DFT and TD-DFT calculations support the experimental results. Additional calculations on the unknown platinacycles with X = CO (7) and SO(2) (8) predict a blue-shift for the MLL'CT absorption and emission. Two nearly equal energy triplet minima were located on the DFT triplet surface for 4-6. One of these (4T-6T) has a geometry very similar to the ground-state singlet (as represented by 4-6) and is associated with the emissive (3)MLL'CT excited state. The other triplet-state (4T'-6T') has a distorted structure where the platinacycle ring is twisted out of the Pt((t)Bu(2)bpy) plane. Thermal access to this distorted triplet may be responsible for the loss of photoluminescence in room temperature solutions of 4-6.     

Test of sum rules in nucleon transfer reactions

The quantitative consistency of nucleon transfer reactions as a probe of the occupancy of valence orbits in nuclei is tested. Neutron-adding, neutron-removal, and proton-adding transfer reactions were measured on the four stable even Ni isotopes, with particular attention to the cross section determinations. The data were analyzed consistently in terms of the distorted wave Born approximation to yield spectroscopic factors. Valence-orbit occupancies were extracted, utilizing the Macfarlane-French sum rules. The deduced occupancies are consistent with the changing number of valence neutrons, as are the vacancies for protons, both at the level of <5%. While there has been some debate regarding the true "observability" of spectroscopic factors, the present results indicate that empirically they yield self-consistent results.     

Asymptotic Expansions for Closed Orbits in Homology Classes

In this paper, we study the behaviour of the counting function associated to the closed geodesics lying in a prescribed homology class on a compact negatively curved manifold. Our main result is an asymptotic expansion. We also obtain results in the wider context of periodic orbits of Anosov flows.     

A novel approach to the solution of boundary-layer problems

By replacing a differential equation boundary-layer problem by its discrete lattice equivalent we are able to treat the resulting equation as a regular perturbation problem. We obtain the solution on the lattice as a regular perturbation series in inverse powers of the lattice spacing. To obtain the answer to the continuum problem we extrapolate the solution to the lattice problem to zero lattice spacing. This extrapolation, which is a Padé-like procedure, yields good numerical results for a wide range of problems.     

On the Hartshorne-Speiser-Lyubeznik theorem about Artinian modules with a Frobenius action

Let be a commutative Noetherian local ring of prime characteristic. The purpose of this paper is to provide a short proof of G. Lyubeznik's extension of a result of R. Hartshorne and R. Speiser about a module over the skew polynomial ring (associated to and the Frobenius homomorphism , in the indeterminate ) that is both -torsion and Artinian over .

     

Platinum and palladium imido and oxo complexes with small natural bite angle diphosphine ligands

Treatment of L(2)MCl(2) (M = Pt, Pd; L(2) = Ph(2)PCMe(2)PPh(2) (dppip), Ph(2)PNMePPh(2) (dppma)) with AgX (X = OTf, BF(4), NO(3)) in wet CH(2)Cl(2) yields the dinuclear dihydroxo complexes [L(2)M(mu-OH)](2)(X)(2), the mononuclear aqua complexes [L(2)M(OH(2))(2)](X)(2), the mononuclear anion complexes L(2)MX(2), or mixtures of complexes. Addition of aromatic amines to these complexes or mixtures gives the dinuclear diamido complexes [L(2)Pt(mu-NHAr)](2)(BF(4))(2), the mononuclear amine complexes [L(2)M(NH(2)Ar)(2)](X)(2), or the dinuclear amido-hydroxo complex [Pt(2)(mu-OH)(mu-NHAr)(dppip)(2)](BF(4))(2). Deprotonation of the Pd and Pt amine or diamido complexes with M'N(SiMe(3))(2) (M' = Li, Na, K) gives the diimido complexes [L(2)M(mu-NAr)](2) associated with M' salts. Structural studies of the Li derivatives indicate association through coordination of the imido nitrogen atoms to Li(+). Deprotonation of the amido-hydroxo complex gives the imido-oxo complex [Pt(2)(mu-O)(mu-NAr)(dppip)(2)].LiBF(4).LiN(SiMe(3))(2), and deprotonation of the dppip Pt hydroxo complex gives the dioxo complex [Pt(mu-O)(dppip)](2).LiN(SiMe(3))(2).2LiBF(4).     

Preface

<正>These two special issues of Acta Mathematica Scientia are dedicated to ProfessorJames Glimm on the occasion of his seventy-fifth birthday.     

Surface modification by ion chemical and physical erosion

Physical and chemical ion erosion surface interactions are observed for various elements and composite materials such as Si, B, C, TiB₂, WCCo cermet, and stainless steel which have been bombarded by low energy (50–1800 eV) hydrogen ions. Extrapolations of hydrogen erosion yields to zero hydrogen ion energy indicate that compounds or elements which are capable of forming volatile compounds with hydrogen undergo selective removal from surface and near surface regions. Auger depth profiling indicates that carbon can be selectively removed from near surface regions of cemented carbides and carburized stainless steel. Similarly, boron can be selectively removed from TiB₂. The results of this study may be extended to a variety of materials in which surface composition modifications are of interest.     

Origin of AIDS: contaminated polio vaccine theory refuted

Despite strong evidence to the contrary, speculation continues that the AIDS virus, human immunodeficiency virus type 1 (HIV-1), may have crossed into humans as a result of contamination of the oral polio vaccine (OPV). This 'OPV/AIDS theory' claims that chimpanzees from the vicinity of Stanleyville--now Kisangani in the Democratic Republic of Congo--were the source of a simian immunodeficiency virus (SIVcpz) that was transmitted to humans when chimpanzee tissues were allegedly used in the preparation of OPV. Here we show that SIVcpz is indeed endemic in wild chimpanzees of this region but that the circulating virus is phylogenetically distinct from all strains of HIV-1, providing direct evidence that these chimpanzees were not the source of the human AIDS pandemic.     

On the photoisomerization of the benzisothiazole portion of ziprasidone

Photostability challenge of ziprasidone in solution shows that the benzisothiazole moiety undergoes isomerization to the corresponding benzthiazole. A model compound, 3-piperazinyl-1,2-benzisothiazole, also undergoes this photoisomerization. Identification of the products has been confirmed by synthesis of the proposed molecules.