Present status of the Technological Laboratory at the LMU Munich

The Technological Laboratory of LMU is undergoing major changes. Most important of them is raising a DLC-Factory’s for diamond-like-carbon (DLC) foils production and a shutdown of the Hot-Lab Facility. Current Laboratory status and development plans are presented in this paper.     

Di-tert-butyldiphosphatetrahedrane as a Source of 1,2-Diphosphacyclobutadiene Ligands

Reactions of di-tert-butyldiphosphatetrahedrane ( 1 ) with cycloocta-1,5-diene- or anthracene-stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2-diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2-diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3-diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2-isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations.     

Physical boundaries within aggregates – differences between amorphous,para‐crystalline,and crystalline Structures

The structural properties of finely divided inorganic materials such as metal and metalloid oxides, silicates or carbonates of both synthetic and natural origin are compared by means of electron microscopy and tomography. The structure of the outer surfaces of various compact or compacted agglomerates may suggest some striking similarities between various amorphous silica on the one hand and crystalline titania and alumina on the other however the details of the interior fine structure are completely different. Inside of the crystalline aggregates of, for example, alumina and titania distinct grain boundaries between the inter‐grown primary crystallites exist. Also physical boundaries between different solid phases and crystalline/amorphous transitions in core/shell structures can occur. No physical grain or phase boundaries were found inside of synthetic amorphous silica or para‐crystalline carbon black thus, the aggregate is the constituent particle. Synthetic amorphous silica from different production technologies (fumed/pyrogenic, precipitated, aerogel, gel) may exhibit different macro‐morphology but distinct similarities of the amorphous silica networks. Computational studies on silica and titania underline the stability of constituent particles and aggregates as observed by means of TEM after dispersing the original materials by ultra‐sonication.     

Selector‐Induced Dynamic Deracemization of a Selectand‐Modified Tropos BIPHEPO‐Ligand: Application in the Organocatalyzed Asymmetric Double‐Aldol‐Reaction

Stereolabile interconverting catalysts open up the possibility of directing enantioselectivity in asymmetric synthesis by formation of diastereomeric complexes with chiral auxiliaries and deracemization. However, the stoichiometrically used auxilliaries can significantly limit the potential applications of such systems. We synthesized a new BIPHEPO tropos ligand containing achiral selectands in the backbone, which forms transient diastereomeric associates with amylose‐tris‐3,5‐dimethylphenyl carbamate as a selector and thus deracemizes. The enantiomerically enriched BIPHEPO obtained was successfully used in the organocatalytic asymmetric double aldol addition of substituted methyl ketones to form benzaldehyde. This strategy combines an on‐column deracemization with the high stereoinduction of chiral biarylphosphineoxides and opens up new possibilities in the field of self‐amplified asymmetric syntheses.     

Polymers with indan units

Cationic polymerisation of 1, 4-diisopropenyl benzene, 1, 4-(2-chloro-isopropyl)benzene and related compounds yields soluble polymers with repeating units of indan. High performance polymers with indan units are available via nucleophilic substitution of halogenated aromatic monomers containing a central indan element, which are synthesized from 1, 1, 3-trimethyl-3-phenylindan via Friedel-Crafts-reaction with corresponding halogenated acyl- and sulfonyl chlorides.     

Time-of-flight studies of emission of μt from frozen hydrogen films

In recent TRIUMF experiments, a μ^- beam is stopped in a solid hydrogen film with a small fraction of T₂. The Ramsauer-Townsend (RT) mechanism allows μt to escape into vacuum with a few eV of energy. To study the emission process, an imaging system was used to determine the position of muon decays. Experimental histograms are in good agreement with a Monte Carlo simulation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electronic properties of CuO 2 -planes: A DMFT study

We study one-particle spectra and the electronic band-structure of a CuO ₂ -plane within the three-band Hubbard model. The Dynamical Mean-Field Theory (DMFT) is used to solve the many particle problem. The calculations show that the optical gap is given by excitations from the lower Hubbard band into the so called Zhang-Rice singlet band. The optical gap turns out to be considerably smaller than the bare charge transfer energy () for a typical set of parameters, which is in agreement with experiment. We also investigate the dependence of the shape of the Fermi surface on the different hopping parameters t CuO and t OO. A value t OO / t CuO >0 leads to a Fermi surface surrounding the M point. Received 21 September 1998 and Received in final form 8 June 1999     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Peltier cooled PbSe double-heterostructure lasers for IR-gas spectroscopy

PbS−PbSe−PbS double-heterostructure lasers have been pulse-operated at about 200 K mounted on 4 stage thermoelectric coolers. Emitting at a wavelength of about 5.5 μm they could be used for NO gas spectroscopy. Operation temperatures of up to 230 K have been achieved with structures consisting ofn-type PbS substrates and epitaxial layers ofn-type PbSe and Tl dopedp-type PbS. The temperature dependence of the threshold current density and the emission wavelength of these DH-lasers was compared with PbSe-homojunction lasers. The use of a germanium etalon for a quick evaluation of the spectral quality of the emitted radiation is described.