Direct Observation of Fine Structure Transitions in a Paramagnetic Nickel(II) Complex Using Far-Infrared Magnetic Spectroscopy: A New Method for Studying High-Spin Transition Metal Complexes

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• 作者：Suriyakan Vongtragool ; Boris Gorshunov ; Martin Dressel ; J. Krzystek ; David M. Eichhorn ; and Joshua Telser
• 刊名：Inorganic Chemistry
• 出版年：2003
• 出版时间：March 24, 2003
• 年：2003
• 卷：42
• 期：6
• 页码：1788 - 1790
• 全文大小：74K
• 年卷期：v.42,no.6(March 24, 2003)
• ISSN：1520-510X

文摘

Novel far-infrared (FIR) absorption spectroscopy in conjunction withmultiple, fixed external magnetic fields (FIR magnetic spectroscopy,FIRMS) has been used to investigate pseudotetrahedral complexeswith the formula M(PPh₃)₂Cl₂ (M = Ni, Zn; Ph = C₆H₅). Crystalstructures have been reported for the Ni complex; we report thestructure of the Zn complex. Transmission spectra at 5 K of Ni(PPh₃)₂Cl₂ (S = 1) at zero magnetic field exhibit absorption bandsat 11.41, 15.28, and 23.0 cm^-1. The two lower frequency bandsshow great sensitivity to external magnetic field, and their fielddependence is as expected for electron spin transitions allowingprecise determination of the following parameters: D =13.35(1) cm^-1, E = 1.93(1) cm^-1, g_x,y = 2.20(1), g_z = 2.00(1).Corresponding spectra of Zn(PPh₃)₂Cl₂ (S = 0) exhibit bands onlyat >20 cm^-1, which show no field dependence. FIRMS is apromising technique for direct investigation of the electronicstructure of high-spin transition metal complexes.