Mechanisms of Exchange Modulation in Trimethylenemethane-type Biradicals: The Roles of Conformation and Spin Density

Journal of the American Chemical Society

Volumn 125, Issue 50, 2003, Pages 15426-15432

  Shultz, David A ^a   Fico Jr , Rosario M ^a   Lee, Hyoyoung ^a,d   Kampf, Jeff W ^b   Kirschbaum, Kristin ^c   Pinkerton, A Alan ^c   Boyle, Paul D ^a  

^a NORTH CAROLINA STATE UNIVERSITY   (United States)

^b UNIVERSITY OF MICHIGAN   (United States)

^c UNIVERSITY OF TOLEDO   (United States)

^d Electronics and Telecommunications Research Institute (ETRI)   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; FERROMAGNETISM; MAGNETIC PROPERTIES; MOLECULAR STRUCTURE;

SPIN DENSITY;

ORGANIC COMPOUNDS;

CARBON; CYCLOPROPANE DERIVATIVE; FERROMAGNETIC MATERIAL; PHENYL GROUP; RADICAL; TRIMETHYLENEMETHANE; UNCLASSIFIED DRUG;

ACCELERATION; ARTICLE; CHEMICAL BOND; CHEMICAL STRUCTURE; CONFORMATION; DENSITY; MAGNETISM; TORSION;

EID: 0348110658     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja037787o     Document Type: Article

References (49)

1. Shultz, D. A. Conformational Exchange Modulation in Trimethylene-methane (TMM)-Type Biradicals. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999.
2. Dei, A.; Gatteschi, D.; Sangregorio, C.; Sorace, L.; Vaz, M. G. F. Inorg. Chem. 2003, 42, 1701-1706.
3. Fujita, J.; Tanaka, M.; Suemune, H.; Koga, N.; Matsuda, K.; Iwamura, H. J. Am. Chem. Soc. 1996, 118, 9347-9351.
4. Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047-3048.
5. Adam, W.; van Barneveld, C.; Bottle, S. E.; Engert, H.; Hanson, G. R.; Harrer, H. M.; Heim, C.; Nau, W. M.; Wang, D. J. Am. Chem. Soc. 1996, 118, 3974-3975.
6. Fang, S.; Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 6727-6731.
7. Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273-13283.
8. Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847-850.
9. Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180-181.
10. Kaftory, M.; Nugiel, D. A.; Biali, S. E.; Rappoport, Z. J. Am. Chem. Soc. 1989, 111, 8181-8191.
11. Shultz, D. A.; Fico, R. M., Jr.; Bodnar, S. H.; Kumar, R. K.; Vostrikova, K. E.; Kampf, J. W.; Boyle, P. D. J. Am. Chem. Soc. 2003, 125, 11761-11771.
12. Streitwieser, A., Jr. Molecular Orbital Theory for Organic Chemists; Wiley & Sons: New York, 1961.
13. Anderson, P. W. Phys. Rev. 1959, 115, 2-13.
14. Hatfield, W. E. Properties of Condensed Compounds (Compounds with Spin Exchange). In Theory and Applications of Molecular Paramagnetism; Boudreaux, E. A., Mulay, L. N., Eds.; Wiley-Interscience: New York, 1976; Chapter 7, pp 381-385.
15. Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587-4594.
16. Borden, W. T. Diradicals; Wiley: New York, 1982.
17. Dougherty, D. A. Acc. Chem. Res. 1991, 24, 88-94.
18. Rajca, A. Chem. Rev. 1994, 94, 871-893.
19. Borden, W. T.; Iwamura, H.; Berson, J. A. Acc. Chem. Res. 1994, 27, 109-116.
20. Shultz, D. A.; Boal, A. K.; Lee, H.; Farmer, G. T. J. Org. Chem. 1999, 64, 4386-4396.
21. Matsumoto, T.; Ishida, T.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1992, 114, 9952-9959.
22. Matsumoto, T.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1992, 114, 5448-5449.
23. Mugnoli, A.; Simonetta, M. J. Chem. Soc., Perkin Trans. 2 1976, 1831-1835.
24. Shultz, D. A.; Fico, R. M., Jr.; Boyle, P. D.; Kampf, J. W. J. Am. Chem. Soc. 2001, 123, 10403-10404.
25. Shultz, D. A.; Boal, A. K.; Farmer, G. T. J. Am. Chem. Soc. 1997, 119, 3846-3847.
26. The term TLS derives from names of the tensors from a rigid body motion analysis of the individual atomic ADPs. The T refers to the translational tensor, the L refers to the librational tensor, and the S refers to the screw tensor, which represents the correlation between the translational and librational motions.
27. Schomaker, V.; Trueblood, K. N. Acta Crystallogr. 1968, B24, 63-76.
28. Dunitz, J. D.; Schomaker, V.; Trueblood, K. N. J. Phys. Chem. 1988, 92, 856-867.
29. Dunitz, J. D.; White, D. N. J. Acta Crystallogr. 1973, A29, 93-94.
30. 1/2.
31. See Supporting Information for all magnetic susceptibility plots and fits.
32. Kahn, O. Molecular Magnetism; VCH: New York, 1993.
33. Bleaney, B.; Bowers, K. D. Proc. R. Soc. London 1952, A214, 451-465.
34. O'Connor, C. J. Prog. Inorg. Chem. 1982, 29, 203-283.
35. Caneschi, A.; Dei, A.; Mussari, C. P.; Shultz, D. A.; Sorace, L.; Vostrikova, K. E. Inorg. Chem. 2002, 41, 1086-1092.
36. There is no pattern to the variation in the zJ′ term within our series of biradicals. Although we have no explanation, our observation is consistent with the lack of a pattern noted by Veciana et al.: Veciana, J.; Cirujeda, J.; Novoa, J. J.; Deumal, M. Supramolecular Architectures and Magnetic Interactions in Crystalline α-Nitronyl Nitroxide Radicals. In Magnetic Properties of Organic Materials; Lahti, P. M., Ed.; Marcel Dekker: New York, 1999; pp 573-600.
37. Hatfield, W. E.; Helms, J. H. Mater. Sci. 1991, 17, 21-31.
38. Georges, R.; Borras-Almenar, J. J.; Coronado, E.; Curely, J.; Drillon, M. One-dimensional Magnetism: An Overview of the Models. In Magnetism: Molecules to Material, Models and Experiments; Miller, J. S., Drillon, M., Eds.; Wiley-VCH: New York, 2001; pp 1-47.
39. Karplus, M. J. Am. Chem. Soc. 1963, 85, 2870-2871.
40. 2 give a J-value that falls directly on the line in Figure 7 using the "undimerized" crystallographic torsion angles.
41. 2 curve has relatively little slope, so changes in J for this range of torsion are expected to be minimal.
42. The fit routine gives A = 44 ± 3 and B = -17 ± 2.
43. Aurich, H. G.; Hahn, K.; Stork, K.; Weiss, W. Tetrahedron 1977, 33, 969-975.
44. Shultz, D. A.; Gwaltney, K. P.; Lee, H. J. Org. Chem. 1998, 63, 769-774.
45. Wheeler, D. E.; Rodriquez, J. H.; McCusker, J. K. J. Phys. Chem. A 1999, 103, 4101-4112.
46. Jacobs, S. J.; Shultz, D. A.; Jain, R.; Novak, J.; Dougherty, D. A. J. Am. Chem. Soc. 1993, 115, 1744-1753.
47. Rajca, A. High-Spin Polyradicals. In Magnetic Properties of Organic Materials; Lahti, P., Ed.; Marcel Dekker: New York, 1999: pp 345-359.
48. Equation 3 is related to McConnell's intermolecular exchange coupling model: McConnell, H. M. J. Chem. Phys. 1963, 39, 1910.
49. j from eq 3.