Prescription for Stabilization of Ferromagnetic Exchange in Molecular Solids via Admixing of the Ground State with a Virtual Charge-Transfer Excited State

Journal of the American Chemical Society

Volumn 109, Issue 13, 1987, Pages 3850-3855

  Miller, Joel S ^a   Epstein, Arthur J ^b  

^a DUPONT COMPANY   (United States)

^b OHIO STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000408841     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00247a006     Document Type: Article

References (25)

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5. Miller, J. S.; Calabrese, J. C.; Bigelow, R. W.; Epstein, A. J.; Zhang, R. W.; Reiff, W. M. J. Chem. Soc., Chem, Commun. 1986, 1026–1028. (b) Miller, J. S.; Calabrese, J. C.; Rommelmann, H.; Chittapeddi, S. R.; Zhang, R. W.; Reiff, W. M.; Epstein, A. J. J. Am. Chem. Soc. 1987, 109, 769–781. (7) Miller, J. S.; Reiff, W. M.; Zhang, J. H., submitted for publication. (8) Breslow, R. Pure Appl. Chem. 1982, 54, 927–938. Breslow, R.; Jaun, B.; Klutz, R. Q.; Xia, C. Z. Tetrahedron 1982, 38, 863–867.
6. Hund's rule was originally proposed for atoms (e.g., McWeeny, R. Coulson's Valence; Oxford University Press: 1979; pp 102-103); however, it was later successfully applied to molecules and biradicals (e.g., Lahti, P. M.; Rossi, A.; Berson, J. A. J. Am. Chem. Soc. 1985,107, 4362–4363. Seeger, D. E.; Lahti, P. M.; Rossi, A.; Berson, J. A. J. Am. Chem. Soc. 1986, 108, 1251–1265 and ref 11a).
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13. Miller, J. S.; Epstein, A. J., unpublished results.
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16. The postulated so-called Buckminsterfullerene, C60, with Ih symmetry (Kroto, H. W.; Heath, J. R.; O'Brian, S. C.; Curl, R. F.; Smalley, R. E. Nature (London) 1985, 318, 162–163) when oxidized or reduced should possess a q9or t5 electron configuration, respectively (Hale, P. D. J. Am. Chem. Soc. 1986, 108, 6087–6088). Since the center cavity of the C60 species can accept a small cation or anion, the reduced or oxidized C60 may exhibit cooperative magnetic properties in the solid state.
17. Accidentally degenerate POMO's for organic compounds are rare and limited to triplet carbenes (e.g., Hoffmann, R.; Zeiss, G. D.; van Dine, G. W. J. Am. Chem. Soc. 1968, 90, 1485–1499. Humphreys, R. W. R.; Arnold, D. R. Can. J. Chem. 1977, 55, 2286–2291. McMahon, R. J.; Chapman, O. C. J. Am. Chem. Soc. 1986, 108, 1713-1714.) and higher spin multiplicity polycarbeneslb,lcwith less than D2d symmery (e.g., Seeger, D. E.; Berson, J. A. J. Am. Chem. Soc. 1983, 105, 5146–5147. Rule, M.; Matlin, A. R.; Seger, D. E.; Hilinski, E. F.; Dougherty, D. A.; Berson, J. A. Tetrahedron 1982, 38, 787-798) and ref 29.
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20. Previous work1a,6suggests that a stable triplet may not be a necessary component for an organic ferromagnet; a stable doublet with a virtually accessible triplet capable of admixing with ground state, as observed for [Fe111(C5Me5)2•+[TCNE]•¯, should suffice.
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