Iodide-conducting polymer electrolytes based on poly-ethylene glycol and MgI2: Synthesis and structural characterization

Vittadello, Michele,Waxman, David I.,Sideris, Paul J.,Gan, Zhehong,Vezzù, Keti,Negro, Enrico,Safari, Ahmad,Greenbaum, Steve G.,Di Noto, Vito

, p. 112 - 122 (2011)

A major obstacle for a viable technological development of dye sensitized solar cells (DSSCs) is still the synthesis of a high performance iodide-conducting polymer electrolyte. Here we present a series of eight electrolytic complexes with formula PEG1000/(MgI2)x(I 2)y (0.0038 ≤ x ≤ 0.5801, 0 ≤ y ≤ 0.0636). The synthesis involves the preparation of a disordered form of MgI2 by a metallorganic route, which enables us to dissolve high amounts of salt in the chosen polymer host. The thermal analysis of the resulting polymer electrolytes was performed using modulated differential scanning calorimetry measurements. Vibrational studies were carried out using medium FT-IR, far FT-IR and FT-Raman. The variation of the CO and OH stretching modes in the medium infrared, as a function of the mole-to-mole ratio nMg/nO, was investigated by Gaussian decomposition to provide insight into the polymer-polymer and salt-polymer interactions in these materials. The FT-Raman spectra confirmed and complemented the vibrational assignment. The conductivity study of these systems was performed by electrical spectroscopy in the frequency interval 10 mHz-10 MHz. The direct current conductivity (σDC) profiles versus the reciprocal temperature exhibited a Vo?gel-Tamman-Fu?lcher (VTF) behavior. The best σDC at 50°C was 5 × 10-5 S cm-1. The overall results indicate the presence of bivalent, monovalent and neutral species, Mg2+, [MgI]+ and MgI2, respectively, which participate in the conduction process. These results are consistent with what was previously observed in PEG400-based systems doped with δ-MgCl2. The presence of at least one Mg site containing a distribution in parameters was observed using 25Mg solid state magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The site has been assigned to a Mg complex involving the coordination by oxygen atoms of the polymer backbone.

Intramolecular Alkene Hydroamination with Hybrid Catalysts Consisting of a Metal Salt and a Neutral Organic Base

Fischer, Christian A.,Harder, Sjoerd,Langer, Jens,Nguyen, D. Thao,Penafiel, Johanne,R?sch, Andreas,Stegner, Philipp C.,Wiesinger, Michael

, p. 3387 - 3394 (2020)

Hybrid catalysts consisting of alkaline earth iodides (AeI2) and the Schwesinger base tBuP4 catalyse the intramolecular alkene hydroamination of H2C=CHCH2CR2CH2NH2 [CR2/sub

Total Synthesis of Actinorhodin

Ninomiya, Mamiko,Ando, Yoshio,Kudo, Fumitaka,Ohmori, Ken,Suzuki, Keisuke

, p. 4264 - 4270 (2019)

The enantioselective total synthesis of actinorhodin (1) is described. The synthesis features 1) dual benzyne reactions en route to the monomer, 2) the trans-selective installation of the side chain, and 3) a regioselective oxidative dimerization.

Mason, C. F.,Farr, J. D.,Bowman, M. G.

, p. 799 - 804 (1980)

Crystal structures of hydrates of simple inorganic salts. I. Water-rich magnesium halide hydrates MgCl2·8H2O, MgCl 2·12H2O, MgBr2·6H2O, MgBr2·9H2O, MgI2·8H2O and MgI2·9H2O

Hennings, Erik,Schmidt, Horst,Voigt, Wolfgang

, p. 1292 - 1300 (2013)

The previously reported structures of the hydrates of simple inorganic salts that crystallize at room temperature are generally well determined. This is not true for water-rich hydrates, which crystallize at temperatures below 273 K. In this series, investigations of the crystal structures of water-rich hydrates crystallized from aqueous solutions at low temperatures are presented. Reported herein are the structures of a set of magnesium salts. Crystals of MgCl2·8H2O (magnesium dichloride octahydrate), MgCl2·12H2O (magnesium dichloride dodecahydrate), MgBr2·6H2O (magnesium dibromide hexahydrate), MgBr2·9H2O (magnesium dibromide nonahydrate), MgI2·8H2O (magnesium diiodide octahydrate) and MgI2·9H2O (magnesium diiodide nonahydrate) were grown from their aqueous solutions at temperatures below 298 K according to the solid-liquid phase diagrams. All structures are built up from Mg(H 2O)6 octahedra. Dimensions and angles in the hexaaqua cation complexes are very similar and variation is not systematic. The anions are incorporated into a specific network of O-H...X hydrogen bonds.

Redox active aluminium(iii) complexes convert CO2 into MgCO 3 or CaCO3 in a synthetic cycle using Mg or Ca metal

Myers, Thomas W.,Berben, Louise A.

, p. 4175 - 4177 (2013)

Redox-active Group 13 molecules possess the unusual combination of concomitant redox and acid-base reactivity. These combined properties enable regeneration of a metal hydroxide complex in a cycle for conversion of CO 2 into carbonate salts. Reaction of (IP-) 2Al(OH) (M = Al, Ga) with 1 atm of CO2 affords [(IP -)2Al]2(μ2κ1: κ2-OCO2). Subsequent reduction affords MgCO 3 or CaCO3 and two equivalents of [(IP2-) 2Al]-, which can be reoxidized to (IP-) 2Al(OH) to close a cycle.

Efficient demethylation of aromatic methyl ethers with HCl in water

Bomon, Jeroen,Bal, Mathias,Achar, Tapas Kumar,Sergeyev, Sergey,Wu, Xian,Wambacq, Ben,Lemière, Filip,Sels, Bert F.,Maes, Bert U. W.

supporting information, p. 1995 - 2009 (2021/03/26)

A green, efficient and cheap demethylation reaction of aromatic methyl ethers with mineral acid (HCl or H2SO4) as a catalyst in high temperature pressurized water provided the corresponding aromatic alcohols (phenols, catechols, pyrogallols) in high yield. 4-Propylguaiacol was chosen as a model, given the various applications of the 4-propylcatechol reaction product. This demethylation reaction could be easily scaled and biorenewable 4-propylguaiacol from wood and clove oil could also be applied as a feedstock. Greenness of the developed methodversusstate-of-the-art demethylation reactions was assessed by performing a quantitative and qualitative Green Metrics analysis. Versatility of the method was shown on a variety of aromatic methyl ethers containing (biorenewable) substrates, yielding up to 99% of the corresponding aromatic alcohols, in most cases just requiring simple extraction as work-up.