Isolation and characterization of phenyl viologen as a radical cation and neutral molecule

被引：111

作者：

Porter, WW

Vaid, TP ^{[1
]}

机构：

[1] Washington Univ, Ctr Mat Innovat, St Louis, MO 63130 USA

[2] Washington Univ, Dept Chem, St Louis, MO 63130 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2005年 / 70卷 / 13期

关键词：

D O I：

10.1021/jo050328g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The chemical synthesis, isolation, and characterization of phenyl viologen (PV) as a dication, radical cation, and neutral species are described. Single-crystal X-ray diffraction of PV(2+)2Cl(-)center dot 2H(2)O and PV center dot+PF(6)(-center dot)pyridine reveals the expected differences in bond lengths and also a structural change from two coplanar central rings in PV center dot+ to a twist of 36 degrees between the two central rings in PV2+. The phenyl viologen radical cation exhibits behavior characteristic of many radical cations, including weak pi-dimerization in the solid state and reversible pi-dimerization in solution. Electrical conductivity measurements of neutral phenyl viologen, the first such measurements of a neutral viologen, reveal that it is a significantly better conductor than the radical cation. Differences in geometric relaxation during charge transfer offer a possible explanation for the higher conductivity of the neutral viologen.

引用

页码：5028 / 5035

页数：8

共 36 条

[1] Monk P.M.S., The Viologens, (1998)
[2] Bird C.L., Kuhn A.T., Chem. Soc. Rev., 10, pp. 49-82, (1981)
[3] Monk P.M.S., Mortimer R.J., Rosseinsky D.R., Electrochromism: Fundamentals and Applications, (1995)
[4] Jang S.S., Jang Y.H., Kim Y.-H., Goddard W.A.I., Flood A.H., Laursen B.W., Tseng H.-R., Stoddart J.F., Jeppesen J.O., Choi J.W., Steuerman D.W., DeIonno E., Heath J.R., J. Am. Chem. Soc., 127, pp. 1563-1575, (2005)
[5] Johnson C.S., Gutowsky H.S., J. Chem. Phys., 39, pp. 58-62, (1963)
[6] Poizat O., Sourisseau C., Mathey Y., J. Chem. Soc., Faraday Trans. 1, 80, pp. 3257-3274, (1984)
[7] Bookman T.M., Kochi J.K., J. Org. Chem., 55, pp. 4127-4135, (1990)
[8] Kosower E.M., Cotter J.L., J. Am. Chem. Soc., 86, pp. 5524-5527, (1964)
[9] Evans A.G., Evans J.C., Baker M.W., J. Am. Chem. Soc., 99, pp. 5882-5884, (1977)
[10] Evans A.G., Evans J.C., Baker M.W., J. Chem. Soc., Perkin Trans. 2, pp. 1787-1789, (1977)

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