Raman spectral study on the structure of a hydrolytic dimer of the aquavanadium(III) ion

Abstract

in HC1 should greatly reduce the stability of the HC1 antihydrogen-bonded complexes with respect to their HF analogues. This change in relative intensities of the vs and avs absorptions can play a key role in the band assignments of these weak complexes since the absorptions are in the same spectral region. Conclusions UF6 and HC1 interact in solid argon to form a well-defined 1:1 hydrogen-bonded complex, UF6-HC1. The band positions of the UF6-HC1 and the FC1-HC1 complexes were very comparable. As the HC1 aggregation increased, a 1:2 complex, UF6-(HC1)2, was observed and characterized by considering the perturbation of the second HC1 submolecule on the 1:1 complex. In contrast, the codeposition of WF6 and MoF6 with HC1 produced hydrogen-bonded 1:1 complexes and antihydrogen-bonded complexes.WF6 and MoF6 displayed little preference between the different structural arrangements. In addition, the HC1 in the hydrogenbonded and the antihydrogen-bonded complexes activated several WF6 and MoF6 modes that are normally infrared-inactive.

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds

“…542 The dimer in acidic solution favors the bis(µ-oxo) binding mode over the bis(µ-hydroxo) binding mode. [544][545][546] Formation of the trimer [V 3 (OH) 8 …”

A review of electrolyte additives and impurities in vanadium redox flow batteries

“…Precipitation problems and possible consequences of flow restrictions or blockages in the operation of the cell thus became the focus of further detailed investigation. Al- though there have been numerous studies on the chemistries and solubilities of different valent vanadium ions in various aqueous solutions since the 1930s [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] , results relating to the composition of vanadium species in solution and the equilibrium solubilities are rather controversial. These discrepancies are not only due to variations in the solution compositions used but also to the limited duration of the precipitation experiments.…”

Synthesis and Structures of Vanadium(III) and -(IV) Complexes with a Tripodal Quadridentate Ligand Containing Alcoholic and Pyridyl or Imidazolyl Functionality

“…Transition moment calculations indicate that the intense transition in the visible region is ascribable to the e g e u *, a metal-localized *-like transition within M-O-M moiety [34,35] DFT calculations for complex 1 also indicate that the intense visible band originates from the e g e u * transition. In previous work [29], the Raman band due to an antisymmetric V-O-V stretching mode was strongly resonanceenhanced upon excitation on the low-energy side of the intense visible absorption band. Because TD-DFT calculations indicate that this intense band is caused by the nondegenerate transition 12 ( Table 4), it is unlikely that the excited state that is formed by the excitation of the intense band undergoes Jahn-Teller distortion.…”

“…The spectra correspond well with each other, indicating that the solid-state structure was maintained upon dissolution in ethanol. The very intense absorption bands observed in the visible region for the known oxo-bridged dinuclear vanadium(III) complexes (for complex 1, the band at 518 nm with = 2990 mol -1 dm 3 cm -1 ) have been assigned to the ligand-to-metal charge transfer (LMCT) transition of the V(III)-O-V(IIII) moiety based on resonance Raman studies [9,[28][29][30]. This assignment is discussed in greater detail later.…”

“…Based on the resonance Raman studies, this intense band was assigned to a charge transfer transition between the bridging oxo atom and vanadium(III) atom [9,[28][29][30]. A qualitative molecular orbital N2-V1-N4 148.77(13) N7-V2-N9 148.24 (14) diagram for the V(III)-O-V(III) moiety was proposed by Bond et al [28].…”