[M(II)(tcne)2]·xCH2Cl2 (M = Mn, Fe, Co, Ni) molecule-based magnets with T(c) values above 100 K and coercive fields up to 6500 Oe

Angewandte Chemie - International Edition

Volumn 37, Issue 5, 1998, Pages 657-660

  Zhang, Jie ^a   Ensling, Jürgen ^b   Ksenofontov, Vadim ^b   Gütlich, Philipp ^b   Epstein, Arthur J ^c   Miller, Joel S ^a  

^a UNIVERSITY OF UTAH   (United States)

^b JOHANNES GUTENBERG UNIVERSITY   (Germany)

^c OHIO STATE UNIVERSITY   (United States)

Author keywords

Iron; Magnetic properties; Radicals; Tetracyanoethylene

Indexed keywords

EID: 0031901236     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980316)37:5<657::AID-ANIE657>3.0.CO;2-L     Document Type: Article

References (32)

1. Mol. Cryst. Liq. Cryst. 1989, 176 (Proceedings on the Conference on Ferromagnetic and High Spin Molecular Based Materials (Eds.: J. S. Miller, D. A. Dougherty)); NATO ARW Molecular Magnetic Materials, 1991, E198 (Proceedings on the Conference on Molecular Magnetic Materials (Eds.: O. Kahn, D. Gatteschi, J. S. Miller, F. Palacio)); Mol. Cryst. Liq. Cryst. 1993, 232/235 (Proceedings on the Conference on the Chemistry and Physics of Molecular Based Magnetic Materials (Eds.: H. Iwamura, J. S. Miller)); ibid. 1995, 271-274 (Proceedings on the Conference on Molecule-based Magnets (Eds.: J. S. Miller, A. J. Epstein)); ibid. 1997, 305/306 (Proceedings on the Conference on Molecular-Based Magnets (Eds.: K. Itoh, T. Takui, J. S. Miller)); M. M. Turnbull, T. Sugimoto, L. K. Thompson, ACS Symp. Ser. 1996, 644.
2. Mol. Cryst. Liq. Cryst. 1989, 176 (Proceedings on the Conference on Ferromagnetic and High Spin Molecular Based Materials (Eds.: J. S. Miller, D. A. Dougherty)); NATO ARW Molecular Magnetic Materials, 1991, E198 (Proceedings on the Conference on Molecular Magnetic Materials (Eds.: O. Kahn, D. Gatteschi, J. S. Miller, F. Palacio)); Mol. Cryst. Liq. Cryst. 1993, 232/235 (Proceedings on the Conference on the Chemistry and Physics of Molecular Based Magnetic Materials (Eds.: H. Iwamura, J. S. Miller)); ibid. 1995, 271-274 (Proceedings on the Conference on Molecule-based Magnets (Eds.: J. S. Miller, A. J. Epstein)); ibid. 1997, 305/306 (Proceedings on the Conference on Molecular-Based Magnets (Eds.: K. Itoh, T. Takui, J. S. Miller)); M. M. Turnbull, T. Sugimoto, L. K. Thompson, ACS Symp. Ser. 1996, 644.
3. Mol. Cryst. Liq. Cryst. 1989, 176 (Proceedings on the Conference on Ferromagnetic and High Spin Molecular Based Materials (Eds.: J. S. Miller, D. A. Dougherty)); NATO ARW Molecular Magnetic Materials, 1991, E198 (Proceedings on the Conference on Molecular Magnetic Materials (Eds.: O. Kahn, D. Gatteschi, J. S. Miller, F. Palacio)); Mol. Cryst. Liq. Cryst. 1993, 232/235 (Proceedings on the Conference on the Chemistry and Physics of Molecular Based Magnetic Materials (Eds.: H. Iwamura, J. S. Miller)); ibid. 1995, 271-274 (Proceedings on the Conference on Molecule-based Magnets (Eds.: J. S. Miller, A. J. Epstein)); ibid. 1997, 305/306 (Proceedings on the Conference on Molecular-Based Magnets (Eds.: K. Itoh, T. Takui, J. S. Miller)); M. M. Turnbull, T. Sugimoto, L. K. Thompson, ACS Symp. Ser. 1996, 644.
4. Mol. Cryst. Liq. Cryst. 1989, 176 (Proceedings on the Conference on Ferromagnetic and High Spin Molecular Based Materials (Eds.: J. S. Miller, D. A. Dougherty)); NATO ARW Molecular Magnetic Materials, 1991, E198 (Proceedings on the Conference on Molecular Magnetic Materials (Eds.: O. Kahn, D. Gatteschi, J. S. Miller, F. Palacio)); Mol. Cryst. Liq. Cryst. 1993, 232/235 (Proceedings on the Conference on the Chemistry and Physics of Molecular Based Magnetic Materials (Eds.: H. Iwamura, J. S. Miller)); ibid. 1995, 271-274 (Proceedings on the Conference on Molecule-based Magnets (Eds.: J. S. Miller, A. J. Epstein)); ibid. 1997, 305/306 (Proceedings on the Conference on Molecular-Based Magnets (Eds.: K. Itoh, T. Takui, J. S. Miller)); M. M. Turnbull, T. Sugimoto, L. K. Thompson, ACS Symp. Ser. 1996, 644.
5. Mol. Cryst. Liq. Cryst. 1989, 176 (Proceedings on the Conference on Ferromagnetic and High Spin Molecular Based Materials (Eds.: J. S. Miller, D. A. Dougherty)); NATO ARW Molecular Magnetic Materials, 1991, E198 (Proceedings on the Conference on Molecular Magnetic Materials (Eds.: O. Kahn, D. Gatteschi, J. S. Miller, F. Palacio)); Mol. Cryst. Liq. Cryst. 1993, 232/235 (Proceedings on the Conference on the Chemistry and Physics of Molecular Based Magnetic Materials (Eds.: H. Iwamura, J. S. Miller)); ibid. 1995, 271-274 (Proceedings on the Conference on Molecule-based Magnets (Eds.: J. S. Miller, A. J. Epstein)); ibid. 1997, 305/306 (Proceedings on the Conference on Molecular-Based Magnets (Eds.: K. Itoh, T. Takui, J. S. Miller)); M. M. Turnbull, T. Sugimoto, L. K. Thompson, ACS Symp. Ser. 1996, 644.
6. Mol. Cryst. Liq. Cryst. 1989, 176 (Proceedings on the Conference on Ferromagnetic and High Spin Molecular Based Materials (Eds.: J. S. Miller, D. A. Dougherty)); NATO ARW Molecular Magnetic Materials, 1991, E198 (Proceedings on the Conference on Molecular Magnetic Materials (Eds.: O. Kahn, D. Gatteschi, J. S. Miller, F. Palacio)); Mol. Cryst. Liq. Cryst. 1993, 232/235 (Proceedings on the Conference on the Chemistry and Physics of Molecular Based Magnetic Materials (Eds.: H. Iwamura, J. S. Miller)); ibid. 1995, 271-274 (Proceedings on the Conference on Molecule-based Magnets (Eds.: J. S. Miller, A. J. Epstein)); ibid. 1997, 305/306 (Proceedings on the Conference on Molecular-Based Magnets (Eds.: K. Itoh, T. Takui, J. S. Miller)); M. M. Turnbull, T. Sugimoto, L. K. Thompson, ACS Symp. Ser. 1996, 644.
7. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
8. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
9. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
10. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
11. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
12. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
13. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
14. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
15. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
16. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
17. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
18. Reviews: a) A. L. Buchachenko, Russ. Chem. Rev. 1990, 59, 307; O. Kahn, Struct. Bonding (Berlin) 1987, 68, 89; Molecular Magnetism, VCH, New York, 1993; b) A. Caneschi, D. Gatteschi, R. Sessoli, P. Rey, Acc. Chem. Res. 1989, 22, 392; D. Gatteschi, Adv. Mater. 1994, 6, 635; c) J. S. Miller, A. J. Epstein, W. M. Reiff, Acc. Chem. Res. 1988, 21, 114; J. S. Miller, A. J. Epstein, W. M. Reiff, Science 1988, 240, 40; Chem. Rev. 1988, 88, 201; J. S. Miller, A. J. Epstein in New Aspects of Organic Chemistry (Eds.: Z. Yoshida, T. Shiba, Y. Ohsiro), VCH, New York, 1989, p. 237; Angew. Chem. 1994, 106, 399; Angew. Chem. Int. Ed. Engl. 1994, 33, 385; Adv. Chem. Ser. 1995, 245, 161.
19. a) J. M. Manriquez, G. T. Yee, R. S. McLean, A. J. Epstein, J. S. Miller, Science 1991, 252, 1415;
20. b) J. S. Miller, G. T. Yee, J. M. Manriquez, A. J. Epstein in ref. [3d], p. 461 (La Chim. La Ind. 1992, 74, 845);
21. b) J. S. Miller, G. T. Yee, J. M. Manriquez, A. J. Epstein in ref. [3d], p. 461 (La Chim. La Ind. 1992, 74, 845);
22. c) A. J. Epstein, J. S. Miller in ref. [3d], p. 475 (La Chim. La Ind. 1993, 75, 185);
23. c) A. J. Epstein, J. S. Miller in ref. [3d], p. 475 (La Chim. La Ind. 1993, 75, 185);
24. d) Proceedings of Nobel Symposium NS-81 Conjugated Polymers and Related Materials: The Interconnection of Chemical and Electronic Structure, Oxford University Press, Oxford, 1993.
25. J. Zhang, P. Zhou, W. B. Brinckerhoff, A. J. Epstein, C. Vazquez, R. S. McLean, J. S. Miller, ACS Sym. Ser. 1996, 644, 311.
26. G. S. Girolami, G. Wilkinson, A. M. R. Galas, M. Thornton-Pett, M. B. Hursthouse, J. Chem. Soc. Dalton Trans. 1985, 1339.
27. 2.
28. P. Gütlich, R. Link, A. Trautwein in Inorganic Concepts 3: Mössbauer Spectroscopy and Transition Metal Chemistry, Springer, Berlin, 1988, p 19, 56-77.
29. a) J. S. Griffith, The Theory of Transition Metal Ions, Cambridge University Press, Cambridge, 1961, p. 271.
30. .- above 240 K(θ = - 120 K) and strong ferromagnetic coupling between 115 and 185 K (θ ∼ + 100 K).
31. c values.
32. Powder diffraction data: corrected d spacing [Å] (normalized intensity): M = Fe: 7.393 (38), 5.123 (25), 4.425 (100), 3.266 (25), 2.862 (21). 2.462 (21); M = Mn: 7.455 (15), 5.210 (17), 4.470 (100), 3.314 (33), 2.912 (25), 2.494 (23).