A novel thermogravimetric analyser

Mahgerefteh, H; Khoory, H.; Khodaverdian, Alfred

doi:10.1016/0040-6031(94)85197-2

Cited by 4 publications

(1 citation statement)

References 9 publications

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“…The divalent transition-metal sulfate monohydrates [M II (SO 4 )(H 2 O)] (M = Fe, Co, Ni, Cu, and Zn) were prepared by dehydration of the heptahydrate or pentahydrate (copper) sulfate, using literature methods. − In a typical procedure, about 1 g of solid metal sulfate polyhydrate was stirred and heated under an argon flow exiting through an external cold trap. Water evolution was monitored and typically ceased after a few minutes at the following maximal temperatures: Fe, 140 °C; Zn, 150 °C; Cu, 170 °C; Co, 215 °C; Ni, 225 °C.…”

Section: Methodsmentioning

confidence: 99%

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

et al. 2017

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Sulfur K-edge XAS spectra of the monodentate sulfate complexes [MII(itao)(SO4)(H2O)0,1] and [Cu(Me6tren)(SO4)] exhibit well-defined pre-edge transitions at 2479.4 eV, 2479.9 eV, 2478.4 eV, and 2477.7 eV, respectively (M = Co, Ni, Cu), despite having no direct metal-sulfur bond, while the XAS pre-edge of [Zn(itao)(SO4)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO4)] but not of [Cu(Me6tren)(SO4)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Pre-edge transitions also appear in the sulfur K-edge XAS of crystalline [MII(SO4)(H2O)] (M = Fe, Co, Ni, Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin-orbitals of the sulfate ligand, inducing negative spin density at sulfate sulfur. Ground state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand anti-bonding orbitals, producing measureable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS pre-edge features 0.5 to 2 eV below the sulfur rising K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the Cu(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the S and the electron hole provides a new mechanism for the counter-intuitive appearance of pre-edge transitions in the XAS spectra of transition metal oxoanion ligands in the absence of any direct metal-absorber bond. The 2472.1 eV transition is evidence for further radicalization from Cu(II), which extends across an H-bond bridge between sulfate and the itao ligand and involves orbitals at energies below the frontier set. This electronic structure feature provides direct spectroscopic confirmation of the through-bond electron transfer mechanism of redox-active metalloproteins.

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