Synthesis and Hydrogen-Bond Patterns of Aryl-Group Substituted Silanediols and -triols from Alkoxy- and Chlorosilanes

Organosilanols typically show a high condensation tendency and only exist as stable isolable molecules under very specific steric and electronic conditions at the silicon atom. In the present work, various novel representatives of this class of compounds were synthesized by hydrolysis of alkoxy- or chlorosilanes. Phenyl, 1-naphthyl, and 9-phenanthrenyl substituents at the silicon atom were applied to systematically study the influence of the aromatic substituents on the structure and reactivity of the compounds. Chemical shifts in ²⁹Si NMR spectroscopy in solution, correlated well with the expected electronic situation induced by the substitution pattern on the Si atom. ¹H NMR studies allowed the detection of strong intermolecular hydrogen bonds. Single-crystal X-ray structures of the alkoxides and the chlorosilanes are dominated by π-π interactions of the aromatic systems, which are substituted by strong hydrogen bonding interactions representing various structural motifs in the respective silanol structures.     

Exciton‐Vibrational Couplings in Homo‐ and Heterodimer Stacks of Perylene Bisimide Dyes within Cyclophanes: Studies on Absorption Properties and Theoretical Analysis

The optical properties of a series of three cyclophanes comprising either identical or different perylene bisimide (PBI) chromophores were studied by UV/Vis absorption spectroscopy and their distinctive spectral features were analyzed. All the investigated cyclophanes show significantly different absorption features with respect to the corresponding constituent PBI monomers indicating strong coupling interactions between the PBI units within the cyclophanes. DFT calculations suggest a π‐stacked arrangement of the PBI units at close van der Waals distance in the cyclophanes with rotational displacement. Simulations of the absorption spectra based on time‐dependent quantum mechanics properly reproduced the experimental spectra, revealing exciton‐vibrational coupling between the chromophores both in homo‐ and heterodimer stacks. The PBI cyclophane comprising two different PBI chromophores represents the first example of a PBI heterodimer stack for which the exciton coupling has been investigated. The quantum dynamics analysis reveals that exciton coupling in heteroaggregates is indeed of similar strength as for homoaggregates.     

Chemo-, regio-, and enantioselective Pd-catalyzed allylic alkylation of indolocarbazole pro-aglycons

[reaction: see text] Monosubstituted isomerically pure indolopyrrolocarbazole precursors have been prepared via palladium-catalyzed asymmetric allylic alkylation methodology, employing both achiral cyclopentenyl electrophiles and chiral glycal derivatives. Chemoselective allylation of (bis)indole lactam pro-aglycon 3 allows access to N-distally substituted indolopyrrolocarbazole derivatives; glyoxamide precursor 14 provides entry into N-proximally substituted derivatives.     

Perturbation Analysis for the Eigenvalue Problem of a Formal Product of Matrices

We study the perturbation theory for the eigenvalue problem of a formal matrix product A ₁ ^{s 1} ··· A _p ^{s p}, where all A _k are square and s _k {–1, 1}. We generalize the classical perturbation results for matrices and matrix pencils to perturbation results for generalized deflating subspaces and eigenvalues of such formal matrix products. As an application we then extend the structured perturbation theory for the eigenvalue problem of Hamiltonian matrices to Hamiltonian/skew-Hamiltonian pencils.     

Exchangelike effects for closed-shell adsorbates: interface dipole and work function

Based on detailed theoretical analyses, we present, for the first time, direct evidence that the significant interface dipole commonly observed for atoms and molecules physisorbed on metal surfaces originates from exchangelike effects. In the case of Xe, previously proposed contributions from chemical interactions do not play a significant role.     

Tuning high-power laser diodes with as much as 0.38 W of power and M(2) = 1.2 over a range of 32 nm with 3-GHz bandwidth

Gain-guided diode lasers usually have emission wavelengths determined by the manufacturing process, with typically 0.5-1-nm bandwidth. Furthermore, their beam quality is rather poor. We show that external cavities allow for tunable narrow-bandwidth operation of gain-guided diode lasers. At the same time the beam quality is drastically improved; almost diffraction-limited light of more than 200 mW has been achieved over the whole tuning range from 910 to 942 nm with narrow bandwidth.     

Very Large Cyclic Compounds

Very large ring systems, containing more than 50 ring members, are becoming increasingly important in different topics in natural sciences. These so-called gigantocycles differ from smaller macrocycles in physical properties, special structural features and chemical behaviour. This article is meant to be the first summary of such ring systems and a synopsis of the most remarkable examples with their fascinating nano-scaled structures and ingenious synthesis. To restrict the scope of the article, only isolated and completely characterized, monodisperse compounds are presented. Furthermore, attention is mainly directed at organic gigantocycles. Some ultracycles with more than 100 ring members, mainly occurring in polymer chemistry and nature, will also be described.