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The Electronic Ground State of [V(urea)6]3+ Probed by NIR Luminescence, Electronic Raman, and High-Field EPR Spectroscopies

The Electronic Ground State of [V(urea)6]3+ Probed by NIR Luminescence, Electronic Raman, and High-Field EPR Spectroscopies

Rémi Beaulac, Philip L W Tregenna-Piggott, Anne-Laure Barra, Høgni Weihe, Dominique Luneau, Christian Reber

Inorg Chem. 2006 Apr 17;45(8):3399-407.

PMID: 16602800

Abstract:

The electronic structure of a trigonally distorted vanadium(III) complex, [V(urea)6](ClO4)3, and its deuterated analogue, [V(urea-d4)6](ClO4)3 has been investigated with Raman, luminescence, and high-frequency high-field electron paramagnetic resonance spectroscopies and with magnetic measurements. A broad electronic Raman transition is observed at around 1400 cm(-1) and attributed to a transition to the (3)E (D3) component of the (3)T1g (O(h)) ground state. The same splitting is seen in the near-infrared luminescence spectrum in the form of a similarly broad peak at 8450 cm(-1), 1400 cm(-1) lower in energy than the (1)E --> (3)A2 spin-flip transition. Powder high-frequency and high-field electron paramagnetic resonance spectra, magnetic susceptibilities, and magnetization studies give a precise measurement of the zero-field splitting and of the g values in this complex (D = 6.00(2) cm(-1), E = 0.573(6) cm(-1), g(x) = 1.848(2), g(y) = 1.832(4), and g(z) = 1.946(7)). A set of angular overlap model parameters is proposed that reproduces all spectroscopic observations, and an analysis of the influence of the bonding of urea on the trigonal distortion of the complex is given.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP1433110	Urea-d4		1433-11-0	Price

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