Tetrasubstituted Peropyrenes Formed by Reductive Aromatization: Synthesis,Functionalization and Characterization

The chromophore class of 1,3,8,10-tetrasubstituted peropyrenes was effectively synthesized from peropyrenequinone via a Zn-mediated reductive aromatization approach. In one step, a symmetric functionalization of the peropyrene backbone introducing silylethers ( 2 , 3 ), pivaloyl ( 4 ), triflyl ( 5 ) and also phosphinite ( 6 ) groups was established. Furthermore, the potential of using 4 and 5 in transition metal catalysed cross couplings was explored leading to 1,3,8,10-tetraaryl ( 8 - 11 ) and tetraalkynyl ( 7 ) peropyrenes. The influence of various substituents on the optoelectronic properties of these π-system extended peropyrenes was investigated in solid state by means of X-ray crystallography, in solution by means of UV-Vis and fluorescence spectroscopy and by their redox properties studied via cyclic voltammetry. By comparison with DFT and TD-DFT calculations, it could be elucidated that introduction of a broad variety of substituents in such versatile one or two step procedures leads to peropyrenes with easily tunable HOMO and LUMO energies ranging in a gap window of 0.8 eV. The frontier molecular orbital energies identify the target molecules as promising candidates for hole transporting semiconductors.     

Stability of AgIII towards Halides in Organosilver(III) Complexes

The involvement of silver in two-electron Ag^I/Ag^III processes is currently emerging. However, the range of stability of the required and uncommon Ag^III species is virtually unknown. Here, the stability of Ag^III towards the whole set of halide ligands in the organosilver(III) complex frame [(CF₃)₃AgX]⁻ (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable Ag^III−X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh₄][(CF₃)₃AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh₄][(CF₃)₃AgCN] and [PPh₄][(CF₃)₃Ag(N₃)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF₃)₃AgX]⁻ entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSⁿ). The experimental detection of the two series of mixed complexes [CF₃AgX]⁻ and [FAgX]⁻ arising from the corresponding parent species [(CF₃)₃AgX]⁻ demonstrate that the Ag−X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F (145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of Ag^III with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.     

Lateral Metallation and Redistribution Reactions of Sodium Ferrates Containing Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilide Ligands

Alkali-metal ferrates containing amide groups have emerged as regioselective bases capable of promoting Fe−H exchanges of aromatic substrates. Advancing this area of heterobimetallic chemistry, a new series of sodium ferrates is introduced incorporating the bulky arylsilyl amido ligand N(SiMe₃)(Dipp) (Dipp=2,6-iPr₂-C₆H₃). Influenced by the large steric demands imposed by this amide, transamination of [NaFe(HMDS)₃] (HMDS=N(SiMe₃)₂) with an excess of HN(SiMe₃)(Dipp) led to the isolation of heteroleptic [Na(HMDS)₂Fe{N(SiMe₃)Dipp}]_∞ ( 1 ) resulting from the exchange of just one HMDS group. An alternative co-complexation approach, combining the homometallic metal amides [NaN(SiMe₃)Dipp] and [Fe{N(SiMe₃)Dipp}₂] induces lateral metallation of one Me arm from the SiMe₃ group in the iron amide furnishing tetrameric [NaFe{N(SiCH₂Me₂)Dipp}{N(SiMe₃)Dipp}]₄ ( 2 ). Reactivity studies support that this deprotonation is driven by the steric incompatibility of the single metal amides rather than the basic capability of the sodium reagent. Displaying synergistic reactivity, heteroleptic sodium ferrate 1 can selectively promote ferration of pentafluorobenzene using one of its HMDS arms to give heterotrileptic [Na{N(SiMe₃)Dipp}(HMDS)Fe(C₆F₅)]_∞ ( 4 ). Attempts to deprotonate less activated pyridine led to the isolation of NaHMDS and heteroleptic Fe(II) amide [(py)Fe{N(SiMe₃)Dipp}(HMDS)] ( 5 ), resulting from an alternative redistribution process which is favoured by the Lewis donor ability of this substrate.     

A Comprehensive Study on the Full Series of Alkali-Metal Selenocyanates AI[SeCN] (AI=Li−Cs)

The full series of quasibinary alkali-metal selenocyanates was synthesized either by oxidation of the respective cyanides (A=Li−Rb) or by metathesis (A=Cs). For Li[SeCN] only ball-milling and subsequent annealing led to the isolation of the quasibinary selenocyanate. Their structures were refined from single-crystal and powder X-ray data. The respective solid-state IR and Raman spectra were interpreted with the aid of solid-state quantum-mechanical calculations and DSC-TGA measurements allowed for extraction of melting points. Only for Li[SeCN] a possible phase transition was observed that is discussed on the basis of VT-PXRD experiments. It is also the only quasibinary selenocyanate to form a hydrate (Li[SeCN] ⋅ 2H₂O).     

Maximizing Ion Transmission in Differential Mobility Spectrometry

We provide modeling and experimental data describing the dominant ion-loss mechanisms for differential mobility spectrometry (DMS). Ion motion is considered from the inlet region of the mobility analyzer to the DMS exit, and losses resulting from diffusion to electrode surfaces, insufficient effective gap, ion fragmentation, and fringing field effects are considered for a commercial DMS system with 1-mm gap height. It is shown that losses due to diffusion and radial oscillations can be minimized with careful consideration of residence time, electrode spacing, gas flow rate, and waveform frequency. Fragmentation effects can be minimized by limitation of the separation field. When these parameters were optimized, fringing field effects at the DMS inlet contributed the most to signal reduction. We also describe a new DMS cell configuration that improves the gas dynamics at the mobility cell inlet. The new cell provides a gas jet that decreases the residence time for ions within the fringing field region, resulting in at least twofold increase in ion signal as determined by experimental data and simulations.

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On the Nature of Mass Spectrometer Analyzer Contamination

Sample throughput in electrospray ionization mass spectrometry (ESI-MS) is limited by the need for frequent ion path cleaning to remove accumulated debris that can lead to charging and general performance degradation. Contamination of ion optics within the vacuum system is particularly problematic as routine cleaning requires additional time for cycling the vacuum pumps. Differential mobility spectrometry (DMS) can select targeted ion species for transmission, thereby reducing the total number of charged particles entering the vacuum system. In this work, we characterize the nature of instrument contamination, describe efforts to improve mass spectrometer robustness by applying DMS prefiltering to reduce contamination of the vacuum ion optics, and demonstrate the capability of DMS to extend the interval between mass spectrometer cleaning. In addition, we introduce a new approach to effectively detect large charged particles formed during the electrospray ionization (ESI) process.

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Analysis of moisture sorption in lyocell-polypropylene composites

The preparation of composites by thermoforming of intermingled fibre slivers is an efficient method to receive high performance and lightweight materials. Cellulosic fibres have benefits like low density and sustainability but the sorption of water due to the high hydrophilicity of the cellulose requires attention. The swelling of the wet fibres changes the fibre-matrix adhesion and as a consequence, the mechanical strength of the composite is influenced negatively. In this study, the thermoplastic polypropylene was combined with lyocell fibres as reinforcement. Moisture sorption isotherms of cellulose/polypropylene composites were recorded as function of relative humidity. Additionally, the specific surface area was analysed by the Brunauer–Emmett–Teller model. It has been found, that the moisture sorption is influenced by the polypropylene (PP) ratio in the composites. At 60% relative humidity the moisture uptake of the lyocell fibres was reduced from 10.8 to 5.8% for lyocell embedded in a composite with 50% polypropylene. Besides the hysteresis between moisture sorption/desorption cycles was found to be proportional to the increased content of PP. The “Parallel Exponential Kinetics” (PEK) model was used to analyse the kinetics of moisture sorption of these composites in more detail. With the help of the PEK model the sorption/desorption kinetics were described by a fast and slow moisture sorption/desorption process. The capacity for rapid moisture sorption is reduced by the formation of PP layers on the lyocell surface. The share of slow moisture sorption increased with increasing PP content in the composite. The results support understanding of the interaction of water with cellulose containing composites.     

Infrared and NMR Spectroscopic Fingerprints of the Asymmetric H7+O3 Complex in Solution

Infrared (IR) absorption in the 1000–3700 cm⁻¹ range and ¹H NMR spectroscopy reveal the existence of an asymmetric protonated water trimer, H₇⁺O_3, in acetonitrile. The core H₇⁺O₃ motif persists in larger protonated water clusters in acetonitrile up to at least 8 water molecules. Quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations reveal irreversible proton transport promoted by propagating the asymmetric H₇⁺O₃ structure in solution. The QM/MM calculations allow for the successful simulation of the measured IR absorption spectra of H₇⁺O₃ in the OH stretch region, which reaffirms the assignment of the H₇⁺O₃ spectra to a hybrid-complex structure: a protonated water dimer strongly hydrogen-bonded to a third water molecule with the proton exchanging between the two possible shared-proton Zundel-like centers. The H₇⁺O₃ structure lends itself to promoting irreversible proton transport in presence of even one additional water molecule. We demonstrate how continuously evolving H₇⁺O₃ structures may support proton transport within larger water solvates.