Publications by authors named "G O Kostin"

The bi-transition-metal interstitial compounds (BTMICs) are promising for water electrolysis. The previous BTMICs are usually composed of irregular particles. Here, this work shows the synthesis of novel 1D CoMoC-based heterojunction nanowires (1D Co/CoMoC) with diameters about 50 nm and a length-to-diameter ratio about 20 for efficient water electrolysis.

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A new nitro-nitrosyl complex [RuNO(Phen)(NO)OH] (1) was synthesized and characterized by X-ray diffraction, where Phen = 1,10-phenanthroline. The complex was crystallized in two different modifications without (1) and with a solvent molecule of DMF (1a). The photolysis process together with the determination of the quantum yield of NO release was investigated in acetonitrile solution using a special flow-through system for the simultaneous registration of infrared (IR) and optical absorption (UV-vis) spectra under irradiation with 450 nm light.

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The reaction of [RuNO(Py)ClOH] with bipyridine in water-ethanol media results in trans-(NO, OH)-[RuNO(Py)(Bpy)ClOH] with an acceptable yield (60-70%) as hexafluorophosphate salt. Further treatment of the hydroxy-complex with concentrated HF quantitatively leads to trans-(NO, F)-[RuNO(Py)(Bpy)ClF]. Despite the chirality of both coordination spheres, the hexafluorophosphate salts crystallized as racemates.

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X-ray absorption spectroscopy (XAS) is a powerful tool for examining changes of the electronic and molecular structure following light-induced excitation of a molecule. Specifically, this method can be applied to investigate the ground (GS, RuNO) and metastable states (MS1, RuON and MS2, Ruη(NO)) of the nitrosyl ligand (NO), which differ in their coordination mode to the metal. In this work, we report for the first time experimental and theoretical (DFT) Ru L,-edge XA spectra for the octahedral complex trans-[RuNOPyF](ClO) (1, Py = pyridine) in both ground and metastable states.

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Article Synopsis
  • Photoinduced linkage isomers (PLI) of NO in transition-metal nitrosyl compounds can be identified through significant shifts in the (NO) stretching vibration using vibrational spectroscopy.
  • In the study of K[RuClNO], the (NO) stretch shifts by about 150 cm from the N-bound ground state to the oxygen-bound metastable state, and by around 360 cm to the side-on metastable isomer.
  • The research found strong coupling between N-O stretching modes and Ru-N/Ru-O stretching modes, which can be separated to analyze local force constants, revealing that the charge on the NO ligand does not correlate with the frequency shifts observed.
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