[INORG-30]Impressive near-infrared brightness and singlet oxygen generation from strategic lanthanide–porphyrin double-decker complexes in aqueous solution

A series of lanthanide-based double-decker complexes were prepared and characterized with different techniques, especially scanning tunneling microscopy, for determining their conformations. The Ln(III) sandwich structures equipped with side-chain feature superior near-infrared brightness and singlet oxygen generation ability which make them become promising theranostic bio-probes.

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[INORG-29]Carbohydrates extraction from wood-based waste for biofuel production

Cellulose was found to undergo autocatalytic hydrolysis in water with presence of salt using microwave irradiation as heating source1. Wood-based waste contain great amount of cellulose which may also undergo autocatalytic hydrolysis for bio-fuel production. Herein, we discover that the yield of polysaccharides hydrolysis with the presence of salt increases approximately 120 to 250% at 190 oC from different wood-based waste. Moreover, solid residue after hydrolysis can undergo hydrolysis again to increase the total yield. However, the yield is relatively low (approximately 1%) due to temperature limitation of the instrument.

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[INORG-28]Metal glycerolates as heterogeneous catalysts for green biodiesel synthesis

High water content in crude bioethanol deters the efficient catalytic production of biodiesel via transesterification. Manganese glycerolate (MnGly) was explored as water-tolerant heterogeneous catalysts towards biodiesel production, withstanding the presence of 80 wt.% water in ethanol for over 90% conversion. The application of the catalysts in utilizing commercially available crude bioethanol in the presence of 14.1 wt% of ethanol and 10 wt.% of glucose was confirmed to exhibit nearly 90% conversion in 24 hours. The results open up the possibility to simplify the current complicated and energy-intensive purification steps of bioethanol on biodiesel application, ultimately achieving a more sustainable process.

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[INORG-27]Differential adsorption of L- and D-lysine on achiral MFI zeolites as determined by synchrotron X-ray powder diffraction and thermogravimetric analysis

Differential adsorption behaviour of L- and D-Lys over H-ZSM-5 has been observed experimentally by circular dichroism (CD) spectroscopy and thermogravimetric analyses (TGA). The fundamental reason is explained by the structural study based on the Rietveld refinement of the high-resolution synchrotron X-ray powder diffraction (SXRD) data and the density functional theory (DFT) calculation.

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[INORG-25]DFT studies on copper-catalyzed dearomatization of pyridine

A systematic theoretical study has been performed with the aid of density functional theory (DFT) calculations on the mechanism of asymmetric 1,4-dearomatization of free pyridine with styrene and dimethoxy(methyl)silane (HSiMe(OMe)2) catalyzed by copper complexes. Two proposed mechanisms, dearomatization of pyridine catalyzed by cooperation of two copper(I) centers and by one copper(I) are calculated and analyzed. The calculation results indicate that one copper(I) center is capable of catalyzing the dearomatization reaction. The origin of selectivity between 1,2- and 1,4-dearomatization of pyridine and the substituent effect have also been systematically discussed.

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[INORG-24]Solvothermal synthesis of metal imidazolate frameworks with 2-D honeycomb structure

Two-dimensional honeycomb structure frameworks were solvothermal synthesized by benzene halide and aniline with the ratio of metal: ligand: base=1:4:2. The SXRD determines to [Cd(BzIm)2]n·0.25n(solvent) (solvent= chlorobenzene I, fluorobenzene II, and aniline III) were selected to introduced. They are centrosymmetric orthorhombic space group Pbcn with high thermal stability. The solvent sits inside the layers and could be removed without framework collapse.

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[INORG-23]The synthesis of rhenium (VII) bis-vinyl complexes by nucleophilic addition of phosphines to alkynes

The organometallic reactions of alkyne have been studied for decades, including previously reported synthesis of rhenium carbyne and η2-vinyl complexes from reactions of alkynes with rhenium hydride complexes.1 We have recently studied the reactions of the rhenium (III) acetonitrile complex ReCl3(MeCN)(PPh3)2 with a series of aromatic alkynes (H−C≡C−R, e.g. R = phenyl, 2-trifluoromethyl-benzenyl, 3-ethynyl-benzenyl, 4-ethynyl-benzenyl, 4-biphenyl, 4-carbazole-benzenyl). The reactions were found to give rhenium (VII) bis-η2-vinyl complexes 2, as a result of intermolecular nucleophilic attack of triphenylphosphine on the coordinated alkyne. In this presentation, the detailed findings arising from the investigation will be described.

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[INORG-22]1,4-selective hydrovinylation of diene catalyzed by iron diimine catalyst: a computational case study on two-state reactivity

Our DFT study on an example of iron catalyzed 1,4-hydrovinylation of a 1,3-diene with an unactivated olefin reported by Chirik, Schmidt, and coworkers reveals a “two-state reactivity” phenomenon. Using our recently developed Principal Interacting Spin Orbital (PISO) analysis, we found that the two-state reactivity phenomenon could be understood as the interplay between orbital interaction, exchange interaction, and coordination geometry. The singlet state favors the orbital interaction between metal center and substrates, whereas the triplet state structure has higher flexibility that it can isomerize more easily.

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