Search results for "ta116"
showing 10 items of 942 documents
A three-coordinate iron–silylene complex stabilized by ligand–ligand dispersion forces
2016
The structural and bonding properties of a three-coordinate N-heterocyclic silyene (NHSi) complex of the iron(II) amide [Fe{N(SiMe3)2}2] are reported. Computational studies reveal that dispersion forces between the amido SiMe3 substituents and the isopropyl substituents on the NHSi ligand significantly enhance the stability of the complex, along with Fe-to-Si π-backbonding.
Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes
2018
The first-row transition-metal(II) dithiolates M(SAriPr4)2 [AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2; M = Cr (1), Mn (3), Fe (4), Co (5), Ni (6), and Zn (7)] and Cr(SArMe6)2 [2; ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2] and the ligand-transfer reagent (NaSAriPr4)2 (8) are described. In contrast to their M(SAriPr6)2 (M = Cr, Mn, Fe, Co, Ni, and Zn; AriPr6 = C6H3-2,6-(C6H2-2,4,6-iPr3)2) congeners, which differ from 1 and 3-6 in having p-isopropyl groups on the flanking aryl rings of the terphenyl substituents, compounds 1 and 4-6 display highly bent coordination geometries with S-M-S angles of 109.802(2)° (1), 120.2828(3)° (4), 91.730(3)° (5), and 92.68(2)° (6) as well as relatively close metal-flanking …
Size‐Selective Encapsulation of Hydrophobic Guests by Self‐Assembled M 4 L 6 Cobalt and Nickel Cages
2012
Subtle differences in metal-ligand bond lengths between a series of [M(4)L(6)](4-) tetrahedral cages, where M = Fe(II), Co(II), or Ni(II), were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single-crystal X-ray diffraction was used to study the solid-state complexes of the iron(II) and nickel(II) cages.
Influence of Substituent and Benzoannulation on Photophysical Properties of 1-Benzoylmethyleneisoquinoline Difluoroborates
2015
A series of 1-benzoylmethyleneisoquinoline difluoroborates were synthesized, and their photophysical properties were determined. The effect of the substituent and benzoannulation on their properties was investigated to make a comparison with recently published results focused on related quinolines. The photophysical properties of isoquinoline derivatives differ from those of quinolines, and the most pronounced differences are found for the fluorescence quantum yields. Both experimental and theoretical approaches were used to explain the observed photophysical properties.
Enantiomeric Resolution of Asymmetric-Carbon-Free Binuclear Double-Stranded Cobalt(III) Helicates and Their Application as Catalysts in Asymmetric Re…
2018
A series of double-stranded binuclear helicates [Co2(H1)2]4+, [Co2(H2)2]4+, and [Co2(H3)2]4+, derived from monodeprotonated bis-pyridyl hydrazine-based ligands of H21, H22, and H23 with one, two, and three -CH2 spacers, were obtained. These asymmetric-carbon-free racemic helicates were separated into their ΔΔ and ΛΛ enantiomers. The resolved helicates were examined for the first time as enantioselective catalysts in asymmetric benzoylation and nitroaldol reactions.
Structural and metallo selectivity in the assembly of [2 × 2] grid-type metallosupramolecular species: Mechanisms and kinetic control
2011
An unsymmetrical bis(tridentate) ligand LH in which one binding site can be readily deprotonated forms a kinetically inert [Co(III)L(2)](+) complex which can be used as a "corner" species for the "Coupe du Roi" assembly of trans,trans-[Co(2)M(2)L(4)](6+) metallogrids (M = Fe(II), Co(II), Cu(II), Zn(II)). In the mixed Co(III)/Co(II) species, the oxidation states appear to be localised. In solution, the ligand LH forms octacationic, homometallic [2 × 2] grids with the individual labile metal ions Fe(II), Co(II), Cu(II), Zn(II), seemingly as mixtures of all possible isomers arising from the unsymmetrical nature of the ligand. In the solid state, however, [Zn(4)L(4)](CF(3)SO(3))(8)·4CH(3)CN cry…
Two-photon absorption of BF2-carrying compounds: insights from theory and experiment
2017
This communication presents a structure–property study of a few novel pyridine-based difluoroborate compounds with a N–BF2–O core, which exhibit outstanding fluorescence properties. To exploit their potential for two-photon bioimaging, relationships between the two-photon action cross section and systematic structural modifications have been investigated and unravelled.
How to fight multiple enemies : target-specific chemical defences in an aposematic moth
2017
Animals have evolved different defensive strategies to survive predation, among which chemical defences are particularly widespread and diverse. Here we investigate the function of chemical defence diversity, hypothesizing that such diversity has evolved as a response to multiple enemies. The aposematic wood tiger moth (Arctia plantaginis) displays conspicuous hindwing coloration and secretes distinct defensive fluids from its thoracic glands and abdomen. We presented the two defensive fluids from laboratory-reared moths to two biologically relevant predators, birds and ants, and measured their reaction in controlled bioassays (no information on colour was provided). We found that defensive…
Fast pyrolysis of hot-water-extracted and soda-AQ-delignified okra (Abelmoschus esculentus) and miscanthus (miscanthus x giganteus) stalks by Py-GC/MS
2018
Abstract The thermochemical behavior of various samples of okra ( Abelmoschus esculentus ) and miscanthus ( Miscanthus x giganteus ) stalks (initial, hot-water-extracted, and those from sulfur-free delignification) were studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). In all cases, major GC-amenable condensable products were measured semi-quantitatively and classified into several product groups. The formation of these product groups from different feedstock samples with varying mass portions of their structural constituents (carbohydrates and lignin) was investigated at 500 °C and 700 °C with a residence time of 5 s and 20 s. The main product groups were aliphatic comp…
Spectroscopic analysis of hot-water- and dilute-acid-extracted hardwood and softwood chips
2017
Hot-water and dilute sulfuric acid pretreatments were performed prior to chemical pulping for silver/white birch (Betula pendula/B. pubescens) and Scots pine (Pinus sylvestris) chips to determine if varying pretreatment conditions on the original wood material were detectable via attenuated total reflectance (ATR) infrared spectroscopy. Pretreatment conditions varied with respect to temperature (130 °C and 150 °C) and treatment time (from 30 min to 120 min). The effects of the pretreatments on the composition of wood chips were determined by ATR infrared spectroscopy. The spectral data were compared to those determined by common wood chemistry analyses to evaluate the suitability of ATR spe…