Two-photon spectroscopy of SnO2 under hydrostatic pressure

The pressure shift of S excitons in the rutile-type semiconductor tin oxide (SnO₂) is measured by two-photon absorption. From these data the pressure coefficients of the band gap (62.0 meV/GPa) and of the exciton binding energy (0.87 meV/GPa) are determined.     

EPR study of topoisomers of La@C82 and La@C90

An analysis of the temperature dependence of the line width variation of topoisomers (I) and (II) of La@C₈₂ revealed that both molecules exhibit practically identical rotational correlation times from room temperature down to the freezing point of CS₂. Although this result indicates confinement of the metal ion, from the increased line width of¹³C satellites in isomer (II) we conclude that in this molecule there might be increased mobility within a confine volume. Three stable topoisomers of La@C₉₀ were identified for the first time. One of these topoisomers was separated by HPLC technique. We were unable, however, to detect any nuclear spin dependence of the EPR line width even at low temperatures. This might indicate that in this case the ion is no longer confined to a specific binding site, although a more trivial explanation assuming small anisotropies of all hyperfine interactions cannot yet be ruled out.     

Total synthesis of iejimalide B

Iejimalide B, a structurally unique 24-membered polyene macrolide having a previously underutilized mode of anticancer activity, was synthesized according to a strategy employing Julia-Kocienski olefinations, a palladium-catalyzed Heck reaction, a palladium-catalyzed Marshall propargylation, a Keck-type esterification, and a palladium-catalyzed macrolide-forming, intramolecular Stille coupling of a highly complex cyclization substrate. The overall synthesis is efficient (19.5% overall yield for 15 linear steps) and allows for more practical scaled-up synthesis than previously reported strategies that differed in the order of assembly of key subunits and in the method of macrocyclization. The present synthesis paves the way for efficient preparation of analogues for drug development efforts.     

One of the most complex "small molecule structures" ever reported: 16 independent molecules in the asymmetric unit for an ortho-palladated primary amine

The presumably "small molecule structure" of the organopalladium complex rac-PdCl(C(6)H(3)-4-OMe-CHMeNH(2))(py) crystallizes with 16 molecules in the asymmetric unit, a highly unusual situation according to the CSD database. The symmetrically independent residues differ with respect to soft conformational degrees of freedom. Packing in the acetonitrile solvate of the same compound is unexceptional.     

The molecular conformation of pentan‐3‐one studied in cholic acid pentan‐3‐one solvate

The crystal structure of cholic acid–pentan‐3‐one (1/1), C₅H₁₀O·C₂₄H₄₀O₅, has been determined in order to deduce the molecular conformation of the small volatile ketone. Data were collected at 100 K to a resolution of (sin θ)/λ = 0.91 Å⁻¹. The structure contains a hydrogen‐bonded cholic acid host network, forming only van der Waals interactions with the guest pentan‐3‐one molecules. The ketone molecules are disordered on general positions, with two clearly identifiable conformations. The majority conformer exhibits approximate C₂ symmetry and is similar to that recently observed by microwave spectroscopy in the gas phase.     

A unified quantum <Emphasis Type="Italic">SO</Emphasis>(3) invariant for rational homology 3-spheres

Given a rational homology 3-sphere M with |H ₁(M,ℤ)|=b and a link L inside M, colored by odd numbers, we construct a unified invariant I _M,L belonging to a modification of the Habiro ring where b is inverted. Our unified invariant dominates the whole set of the SO(3) Witten–Reshetikhin–Turaev invariants of the pair (M,L). If b=1 and L=∅, I _M coincides with Habiro’s invariant of integral homology 3-spheres. For b>1, the unified invariant defined by the third author is determined by I _M . Important applications are the new Ohtsuki series (perturbative expansions of I _M ) dominating quantum SO(3) invariants at roots of unity whose order is not a power of a prime. These series are not known to be determined by the LMO invariant.     

Synthesis and Spectral Study of Several Solid M3[Eu(2,6-Pyridinedicarboxylate)3] Salts (M=Li+, Na+, K+, Rb+, Cs+, NH4 +, and Pyridinium+)

Abstract

Salts of the [Eu(2,6-pyridinedicarboxylate)₃]^3- complex anion and various monovalent inorganic and organic counterions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, and pyridinium⁺) have been synthesized and studied by emission spectroscopy. The Eu³⁺ ion emission spectra exhibited by these salts have been observed with high resolution (less than 1.0 cm^?1) and at low temperature (77 K). The emission spectra of these compounds indicate that changing the attached counterion does not affect the site symmetry observed by the europium ion beyond slight distortions indicated by small shifts in the energies of the Eu³⁺ electronic levels.