Excited State Tuning of Bis(tridentate) Ruthenium(II) Polypyridine Chromophores by Push–Pull Effects and Bite Angle Optimization: A Comprehensive Experimental and Theoretical Study

The synergy of push–pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the ¹MLCT absorption and the ³MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the ³MLCT excited‐state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC‐tpy)][PF₆]₂, [Ru(ddpd‐NH₂)(EtOOC‐tpy)][PF₆]₂, [Ru(ddpd){(MeOOC)₃‐tpy}][PF₆]₂, and [Ru(ddpd‐NH₂){(EtOOC)₃‐tpy}][PF₆]₂ the combination of the electron‐accepting 2,2′;6′,2′′‐terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron‐donating N,N′‐dimethyl‐N,N′‐dipyridin‐2‐ylpyridine‐2,6‐diamine (ddpd) ligand decorated with none or one NH₂ group enforces spatially separated and orthogonal frontier orbitals with a small HOMO–LUMO gap resulting in low‐energy ¹MLCT and ³MLCT states. The extended bite angle of the ddpd ligand increases the ligand field splitting and pushes the deactivating ³MC state to higher energy. The properties of the new isomerically pure mixed ligand complexes have been studied by using electrochemistry, UV/Vis absorption spectroscopy, static and time‐resolved luminescence spectroscopy, and transient absorption spectroscopy. The experimental data were rationalized by using density functional calculations on differently charged species (charge n=0–4) and on triplet excited states (³MLCT and ³MC) as well as by time‐dependent density functional calculations (excited singlet states).     

The t+n+n system and 5H

The one-proton knockout channel from 6He (240 MeV/u) impinging on a carbon target has been investigated. The triton fragments originating from this channel were detected in coincidence with the two neutrons. A broad structure, peaked at 3 MeV above the t+2n threshold, is observed in the t+n+n-relative energy spectrum. It is shown that this structure is mainly due to a I(pi)=1/2(+) resonance as expected for the 5H ground state, and from the observed angular and energy correlations, being used for the first time in 5H studies, that the neutrons to a large extent occupy the p shell.     

Fragmentation of the chain in the mass spectra of the pyrrolidides of alkylcyclohexanecarboxylic acids

The electron impact mass spectra of the pyrrolidides of both the cis- and trans-octylcyclohexanecarboxylic acids show the structure of the aliphatic chain, despite the steric hindrance of a direct H transfer from the chain to the functional group.     

Effective Polytropic Indices of Anisotropic Planetary Magnetosheath Plasmas with Magnetoacoustic Waves

Magnetosheath models for the planets Earth, Jupiter and Saturn are developed within the frame of the double‐adiabatic Chew‐Goldberger‐Low approximation. It is shown that in all three magnetosheaths slow and fast magnetoacoustic waves are generated, the dispersions of which considerably differ from that of isotropic systems. If slow magnetoacoustic waves exist in the magnetosheaths, then the effective polytropic coefficient of the plasma may be smaller than unity ‐ that means compression of the plasma is accompanied, in the average, by cooling. Such polytropic coefficients are not obtained when fast magnetoacoustic waves are excited (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Operation of a Raman laser in bulk silicon

A Raman laser based on a bulk silicon single crystal with 1.127 μm emission wavelength is demonstrated. The Si crystal with 30 mm length was placed into an external cavity and pumped by a Q-switched Nd:YAG master oscillator power amplifier system. Strong defocusing of the pump and Raman laser beam by free carriers was compensated by an intracavity lens. Raman laser operation with a pulse duration of 2.5 ns was identified by a Raman laser threshold significantly lower than the single-pass stimulated Raman-scattering threshold. Linear absorption losses of the 1.06415 μm pump radiation are strongly reduced by cooling the Si crystal to a temperature of 10 K.     

General Synthesis and Physicochemical Characterisation of a Series of Peptide‐Mimic Lysine‐Based Amino‐Functionalised Lipids

A series of novel malonic acid diamides (second generation) with two long hydrophobic alkyl chains and an alkaline polar head group was synthesised and characterised as a new class of amino‐functionalised lipids. These peptide‐mimic lipids are suitable for polynucleotide transfer. The lipids bear a novel backbone consisting of a lysine unit and a malonic acid unit. Six different head‐group structures, which vary in size and number of amino groups that can be protonated, were attached to the backbone structure. Furthermore, different alkyl chains were used to build the lipophilic part (namely tetradecyl, hexadecyl, and oleyl). Phase transitions of the new compounds in aqueous dispersions at pH 10 were analysed and discussed in terms of head group and alkyl chain variations. The shape and size of the formed aggregates of selected lipid dispersions were investigated by dynamic light scattering and transmission electron microscopy.