Crystallography, magnetic susceptibility, heat capacity, and electrical resistivity of heavy fermion LiV2_2O4_4 single crystals grown using a self-flux technique

Magnetically pure spinel compound ${\rm LiV_2O_4}$ is a rare $d$-electron heavy fermion. Measurements on single crystals are needed to clarify the mechanism for the heavy fermion behavior in the pure material. In addition, it is known that small concentrations ($< 1$ mol%) of magnetic defects in the structure strongly affect the properties, and measurements on single crystals containing magnetic defects would help to understand the latter behaviors. Herein, we report flux growth of ${\rm LiV_2O_4}$ and preliminary measurements to help resolve these questions. The magnetic susceptibility of some as-grown crystals show a Curie-like upturn at low temperatures, showing the presence of magnetic defects within the spinel structure. The magnetic defects could be removed in some of the crystals by annealing them at 700 $^\circ$C\@. A very high specific heat coefficient $\gamma$ = 450 mJ/(mol K${^2}$\@) was obtained at a temperature of 1.8 K for a crystal containing a magnetic defect concentration $n$${\rm_{defect}}$ = 0.5 mol%. A crystal with $n$${\rm _{defect}}$ = 0.01 mol% showed a residual resistivity ratio of 50.Comment: 6 pages, 7 figures, Title modifie

Guanidinium 5,5′‐Azotetrazolate: A Colorful Chameleon for Halogen‐Free Smoke Signals

A progressive halogen‐free multicolored smoke system to obtain white, red, violet, yellow, green, and blue smoke color is presented. The nitrogen‐rich salt guanidinium 5,5′‐azotetrazolate (GZT), which is usually applied as a gas generator or propellant ingredient, was combined with different smoke dyes (Solvent Red 1, Solvent Violet 47, Solvent Green 3, Solvent Yellow 33). These two‐component smoke mixtures offer a convenient and safe multicolor approach without the need for potassium chlorate or any other hazardous material. The common smoke characteristics with respect to burn time/burn rate, yield factor, transfer rate, as well as energetic properties were determined and compared with classic chlorate‐based formulations currently used. To the best of our knowledge, nothing comparable is known in the literature and a completely new research area in modern pyrotechnics is opened

The Flame Emission of Indium from a Pyrotechnical View

Until today, all blue‐colored light‐generating pyrotechnics are still based on copper and a halogen‐source providing the blue‐emitting species copper(I) chloride, copper(I) bromide or copper(I) iodide. The use of indium as a potential halogen‐free blue light emitter in modern pyrotechnics is described. Therefore, metallic indium was introduced as both fuel and colorant in various pyrotechnical formulations including guanidine nitrate or potassium nitrate as oxidizing agent as well as magnesium, hexamethylentetramine and 5‐amino‐1H‐tetrazole as fuel. The effect of incandescence was examined by applying different magnesium contents within the mixtures. Emission spectra and occurring emission lines of indium‐based pyrotechnical compositions were recorded and evaluated for the first time. Since the expected blue flame color could not be completely achieved, the emission of indium was discussed from an academic point of view

Addition of Amines to a Carbonyl Ligand: Syntheses, Characterization, and Reactivities of Iridium(III) Porphyrin Carbamoyl Complexes

Treatment of (carbonyl)chloro(meso-tetra-p-tolylporphyrinato)iridium(III), (TTP)Ir(CO)Cl (1), with excess primary amines at 23 °C in the presence of Na2CO3 produces the trans-amine-coordinated iridium carbamoyl complexes (TTP)Ir(NH2R)[C(O)NHR] (R = Bn (2a), n-Bu (2b), i-Pr (2c), t-Bu (2d)) with isolated yields up to 94%. The trans-amine ligand is labile and can be replaced with quinuclidine (1-azabicyclo[2.2.2]octane, ABCO), 1-methylimidazole (1-MeIm), triethyl phosphite (P(OEt)3), and dimethylphenylphosphine (PMe2Ph) at 23 °C to afford the hexacoordinated carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (for R = Bn: L = ABCO (3a), 1-MeIm (4a), P(OEt)3 (5a), PMe2Ph (6a)). On the basis of ligand displacement reactions and equilibrium studies, ligand binding strengths to the iridium metal center were found to decrease in the order PMe2Ph \u3e P(OEt)3 \u3e 1-MeIm \u3e ABCO \u3e BnNH2 ≫ Et3N, PCy3. The carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = RNH2 (2a,b), 1-MeIm (4a)) undergo protonolysis with HBF4 to give the cationic carbonyl complexes [(TTP)Ir(NH2R)(CO)]BF4 (7a,b) and [(TTP)Ir(1-MeIm)(CO)]BF4 (8), respectively. In contrast, the carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = P(OEt)3 (5a), PMe2Ph (6a,c)) reacted with HBF4 to afford the complexes [(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10), respectively. The carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = RNH2 (2a–d), 1-MeIm (4a), P(OEt)3 (5b), PMe2Ph (6c)) reacted with methyl iodide to give the iodo complexes (TTP)Ir(L)I (L = RNH2 (11a–d), 1-MeIm (12), P(OEt)3(13), PMe2Ph (14)). Reactions of the complexes [(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10) with [Bu4N]I, benzylamine (BnNH2), and PMe2Ph afforded (TTP)Ir(PMe2Ph)I (14), (TTP)Ir[P(OEt)3]I (13), [(TTP)Ir(PMe2Ph)(NH2Bn)]BF4 (16), and trans-[(TTP)Ir(PMe2Ph)2]BF4 (17), respectively. Metrical details for the molecular structures of 4a and17 are reported

Lewis Base Mediated β-Elimination and Lewis Acid Mediated Insertion Reactions of Disilazido Zirconium Compounds

The reactivity of a series of disilazido zirconocene complexes is dominated by the migration of anionic groups (hydrogen, alkyl, halide, OTf) between the zirconium and silicon centers. The direction of these migrations is controlled by the addition of two-electron donors (Lewis bases) or two-electron acceptors (Lewis acids). The cationic nonclassical [Cp2ZrN(SiHMe2)2]+ ([2]+) is prepared from Cp2Zr{N(SiHMe2)2}H (1) and B(C6F5)3 or [Ph3C][B(C6F5)4], while reactions of B(C6F5)3 and Cp2Zr{N(SiHMe2)2}R (R = Me (3), Et (5), n-C3H7 (7), CH═CHSiMe3 (9)) provide a mixture of [2]+ and [Cp2ZrN(SiHMe2)(SiRMe2)]+. The latter products are formed through B(C6F5)3 abstraction of a β-H and R group migration from Zr to the β-Si center. Related β-hydrogen abstraction and X group migration reactions are observed for Cp2Zr{N(SiHMe2)2}X (X = OTf (11), Cl (13), OMe (15), O-i-C3H7 (16)). Alternatively, addition of DMAP (DMAP = 4-(dimethylamino)pyridine) to [2]+ results in coordination to a Si center and hydrogen migration to zirconium, giving the cationic complex [Cp2Zr{N(SiHMe2)(SiMe2DMAP)}H]+ ([19]+). Related hydrogen migration occurs from [Cp2ZrN(SiHMe2)(SiMe2OCHMe2)]+ ([18]+) to give [Cp2Zr{N(SiMe2DMAP)(SiMe2OCHMe2)}H]+ ([22]+), whereas X group migration is observed upon addition of DMAP to [Cp2ZrN(SiHMe2)(SiMe2X)]+ (X = OTf ([12]+), Cl ([14]+)) to give [Cp2Zr{N(SiHMe2)(SiMe2DMAP)}X]+ (X = OTf ([26]+), Cl ([20]+)). The species involved in these transformations are described by resonance structures that suggest β-elimination. Notably, such pathways are previously unknown in early metal amide chemistry. Finally, these migrations facilitate direct Si–H addition to carbonyls, which is proposed to occur through a pathway that previously had been reserved for later transition metal compounds

Nucleophilicity of Neutral versus Cationic Magnesium Silyl Compounds

Charge and ancillary ligands affect the reactivity of monomeric tris(trimethylsilyl)silyl magnesium compounds. Diamine-coordinated (tmeda)Mg{Si(SiMe3)3}Me (tmeda = tetramethylethylenediamine; 2-tmeda) and (dpe)Mg{Si(SiMe3)3}Me (dpe =1,2-N,N-dipyrrolidenylethane; 2-dpe) are synthesized by salt elimination reactions of L2MgMeBr and KSi(SiMe3)3. Compounds 2-tmeda or 2-dpe react with MeI or MeOTf to give MeSi(SiMe3)3 as the product of Si–C bond formation. In contrast, 2-tmeda and 2-dpe undergo exclusively reaction at the magnesium methyl group with electrophiles such as Me3SiI, B(C6F5)3, HB(C6F5)2, and [Ph3C][B(C6F5)4]. These reactions provide a series of neutral, zwitterionic, and cationic magnesium silyl compounds, and from this series we have found that silyl group transfer is less effective with cationic magnesium compounds than neutral complexes

Germination of Range Plant Seeds at Fixed Temperatures

Low temperatures in the 4-10C (39-50F) range were found in the laboratory to delay germination of pasture plants, especially of perenial grasses. Analysis of meteorological data showed temperatures in this range to be prevalent during rainfall periods in the winter (sowing) season in Israel's semi-arid South, and they are considered a critical factor in seeding perennial grasses on arid range. Germination may be improved by agronomic measures, such as plant selection and breeding for cold resistance and seedling vigour, timing of seeding operations, and soil surface treatments to increase soil temperature.This material was digitized as part of a cooperative project between the Society for Range Management and the University of Arizona Libraries.The Journal of Range Management archives are made available by the Society for Range Management and the University of Arizona Libraries. Contact [email protected] for further information.Migrated from OJS platform August 202