Perovskites with the Framework‐Forming Xenon

The Group 18 elements (noble gases) were the last ones in the periodic system to have not been encountered in perovskite structures. We herein report the synthesis of a new group of double perovskites KM(XeNaO₆) (M=Ca, Sr, Ba) containing framework‐forming xenon. The structures of the new compounds, like other double perovskites, are built up of the alternating sequence of corner‐sharing (XeO₆) and (NaO₆) octahedra arranged in a three‐dimensional rocksalt order. The fact that xenon can be incorporated into the perovskite structure provides new insights into the problem of Xe depletion in the atmosphere. Since octahedrally coordinated Xe^VIII and Si^IV exhibit close values of ionic radii (0.48 and 0.40 Å, respectively), one could assume that Xe^VIII can be incorporated into hyperbaric frameworks such as MgSiO₃ perovskite. The ability of Xe to form stable inorganic frameworks can further extend the rich and still enigmatic chemistry of this noble gas.     

Analysis of volatile organic compounds released from the decay of surrogate human models simulating victims of collapsed buildings by thermal desorption–comprehensive two-dimensional gas chromatography–time of flight mass spectrometry

Field experiments were devised to mimic the entrapment conditions under the rubble of collapsed buildings aiming to investigate the evolution of volatile organic compounds (VOCs) during the early dead body decomposition stage. Three pig carcasses were placed inside concrete tunnels of a search and rescue (SAR) operational field terrain for simulating the entrapment environment after a building collapse. The experimental campaign employed both laboratory and on-site analytical methods running in parallel. The current work focuses only on the results of the laboratory method using thermal desorption coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (TD-GC × GC-TOF MS). The flow-modulated TD-GC × GC-TOF MS provided enhanced separation of the VOC profile and served as a reference method for the evaluation of the on-site analytical methods in the current experimental campaign. Bespoke software was used to deconvolve the VOC profile to extract as much information as possible into peak lists. In total, 288 unique VOCs were identified (i.e., not found in blank samples). The majority were aliphatics (172), aromatics (25) and nitrogen compounds (19), followed by ketones (17), esters (13), alcohols (12), aldehydes (11), sulfur (9), miscellaneous (8) and acid compounds (2). The TD-GC × GC-TOF MS proved to be a sensitive and powerful system for resolving the chemical puzzle of above-ground “scent of death”.     

Synthesis and Structural Characterization of Some New Magnesium Formamidinates

[Mg(Form)₂(THF)] [Form = bis(2,6‐dimethylphenyl)formamidinate (XylForm) ( 1 ), bis(2,6‐diethylphenyl)formamidinate, (EtForm) ( 2 ), bis(2,6‐diisopropylphenyl)formamidinate (DippForm) ( 3 )] are conveniently synthesized by treating bis(2,6‐dimethylphenyl)formamidine, bis(2,6‐diethylphenyl)formamidine, or bis(2,6‐diisopropylphenyl)formamidine, respectively, with half an equivalent of dibutylmagnesium in THF. Compounds 1 – 3 are mononuclear species in the solid state with five coordinate central metal atoms. The ¹H NMR chemical shift of the formamidinate formyl proton exhibits a correlation with ligand sterics wherein increasing bulk leads to a shift to higher field.     

Sorption and Separation of Optical Isomers of 2-Butanol by Chiral Porous Coordination Polymers

Theoretical and Experimental Chemistry - It was shown that porous coordination polymers (PCPs) of 3d metals containing chiral centers in fragments of deprotonated (S)-lactic and (R)-aspartic acid...