Abstract
The field of heteropolymetallic systems with magnetic metal centers occupies a crossing point between biology and physics. For instance the Cu(II)-Fe(III) interaction in cytochrome oxidase is of the same nature as the Cu(II)-Mn(II) interaction in a novel system which could be the first molecular ferromagnet. The mechanism of the interaction is discussed, both from a phenomenological view point using a spin Hamiltonian, and from an orbital view point. An orbital model for the isotropic interaction is presented. It is based on the concept of natural magnetic orbitals. The mechanism of the anisotropic and antisymmetric interactions is more briefly treated. The role of the Zeeman perturbation is then considered in relation with the magnetic and EPR properties of the heterobimetallic complexes. Several examples are presented to emphasize that the nature, ferro- or antiferromagnetic of the isotropic interaction is controlled by the symmetry of the magnetic orbitals. The concept of overlap density is introduced. It permits an estimation of the magnitude of the ferromagnetic stabilization in the case of orthogonality of the magnetic orbitals. The Cu(II)-Fe(III) interaction, in relation to the situation encountered in cytochrome oxidase, the Cu(II)-Ni(II) interaction and a few additional selected examples are discussed. A section deals with the case where one of the interacting ions has an orbital degeneracy. Afterwards, the heterotrinuclear complexes are studied. The important concept of regular and irregular spin state structure is developped and the Mn(II)Cu(II)Mn(II) triad is presented as a spectacular example of irregular spin state structure. A section is devoted to the ordered bimetallic chains. The theory is presented, both at a qualitative and quantitative levels and the already reported compounds of this kind are discussed. One of them may be considered as one of the first molecular ferromagnets. The last but one section concerns the systems with even more subtle spin orders. In conclusion, the vast perspectives of this area are outlined.
Preview
Unable to display preview. Download preview PDF.
References
Casellato, U., Vigato, P. A.: Coord. Chem. Rev. 23, 31 (1977)
Groh, E.: Israel J. Chem. 15, 277 (1976/1977)
Lintvedt, R. L., Glick, M. D., Tomlonovic, B. K., Gavel, D. P.: Inorg. Chem. 15, 1646 (1976)
Glick, M. D., Lintvedt, R. L., Gavel, D. P., Tomlonovic, B.: ibid. 15, 1654 (1976)
Lintvedt, R. L., Ahmad, N.: ibid. 21, 2356 (1982)
Coucouvanis, D.: J. Am. Chem. Soc. 92, 707 (1970)
Coucouvanis, D., Baenziger, N. C., Johnson, S. M.: ibid. 95, 3875 (1973)
Coucouvanis, D., Baenziger, N. C., Johnson, S. M.: Inorg. Chem. 13, 1191 (1974)
Coucouvanis, D., Piltingsrud, D.: J. Am. Chem. Soc. 95, 5556 (1973)
Hollander, F. J., Coucouvanis, D.: Inorg. Chem. 13, 2381 (1974)
Caffery, M. L., Coucouvanis, D.: J. Inorg. Nucl. Chem. 37, 2081 (1975)
O'Bryan, N. B., Maier, T. O., Paul, I. C., Drago, R. S.: J. Am. Chem. Soc. 95, 6640 (1973)
Leslie, K. A., Drago, R. S., Stucky, G. D., Kitko, D. J., Breese, J. A.: Inorg. Chem. 18, 1885 (1979)
Moriya, T. in: Magnetism (Rado, G. T., Suhl, H. eds.), Vol. 1, p. 85, New York-London, Academic Press 1963
Kahn, O. in: Magneto-Structural Correlations in Exchange Coupled Systems (Willett, R. D., Gatteschi, D., Kahn, O. eds.), p. 37, Dordrecht, D. Reidel 1985
Anderson, P. W. in: Magnetism (Rado, G. T., Suhl, H. eds.), Vol. 1, p. 25; New York-London, Academic Press 1963
Hay, P. J., Thibeault, J. C., Hoffmann, R.: J. Am. Chem. Soc. 97, 4884 (1975)
Kahn, O., Briat, B.: J. Chem. Soc. Faraday II, 72, 268 (1976)
Kahn, O., Charlot, M. F.: Nouv. J. Chim. 4, 567 (1980)
Girerd, J. J., Journaux, Y., Kahn, O.: Chem. Phys. Letters 82, 534 (1981)
Van Kalkeren, G., Schmidt, W. W., Block, R.: Physica 97B, 315 (1979)
Girerd, J. J., Charlot, M. F., Kahn, O.: Mol. Phys. 34, 1063 (1977)
Girerd, J. J.: Thèse d'état, Université de Paris Sud 1982
Tola, P., Kahn, O., Chauvel, C., Coudanne, H.: Nouv. J. Chim. 1, 467 (1977)
Moriya, T.: Phys. Rev. B 120, 91 (1960)
Kanamori, J. in: Magnetism (Rado, G. T., Suhl, H. eds.), Vol. 1, p. 127, New York-London, Academic Press 1963
Gatteschi, D., Bencini, A. in: Magneto-Structural Correlations in Exchange Coupled Systems (Willett, R. D., Gatteschi, D., Kahn, O. eds.), p. 241, Dordrecht, D. Reidel 1985
Bencini, A., Gatteschi, D.: Mol. Phys. 47, 161 (1982)
Banci, L., Bencini, A., Gatteschi, D.: J. Am. Chem. Soc. 105, 761 (1983)
Charlot, M. F., Journaux, Y., Kahn, O., Bencini, A., Gatteschi, D., Zanchini, C.: Inorg. Chem. 25, 1060 (1986)
Chao, C. C.: J. Magn. Reson. 10, 1 (1973)
Buluggiu, E., Vera, A.: Z. Naturforsh. 31a, 911 (1976)
Buluggiu, E.: J. Phys. Chem. Solids 41, 1175 (1980)
Scaringe, R. P., Hodgson, D., Hatfield, W. E.: Mol. Phys. 35, 701 (1978)
Griffith, J. S.: Struct. Bonding 10, 87 (1972)
Kahn, O., Galy, J., Journaux, Y., Jaud, J., Morgenstern-Badarau, I.: J. Am. Chem. Soc. 104, 2165 (1982)
Galy, J., Jaud, J., Kahn, O., Tola, P.: Inorg. Chim. Acta 36, 229 (1979)
Julve, M., Verdaguer, M., Charlot, M. F., Kahn, O., Claude, R.: ibid. 82, 5 (1984)
Kahn, O.: Comments Inorg. Chem. 3, 105 (1984)
Crawford, W. H., Richardson, H. W., Wasson, J. R., Hodgson, D. J., Hatfield, W. E.: Inorg. Chem. 15, 2107 (1976)
Landee, C. P., Willett, R. D.: ibid. 20, 2521 (1981)
Ginsberg, A. P., Martin, R. L., Brookes, R. W., Sherwood, R. C.: ibid. 11, 2884 (1972)
Duggan, D. M., Hendrickson, D. N.: ibid. 13, 2929 (1974)
Laskowski, E. J., Felthouse, T. R., Hendrickson, D. N., Long, G.: ibid. 15, 2908 (1976)
Young, K. O., O'Connor, C. J., Sinn, E., Carlin, R. L.: ibid. 18, 804 (1979)
Journaux, Y., Kahn, O.: J. Chem. Soc. Dalton 1575 (1979)
Willett, R. D., Gaura, R. M., Landee, C. P. in: Extended Linear Chain Compounds (Miller, J. S. ed.), Vol. 3, p. 143, New York-London, Plenum Press 1983
Hatfield, W. E., Estes, W. E., Marsch, W. E., Pickens, M. W., Ten Haar, L. W., Weller,iR. R. ie: Extended Linear Chain Compounds (Miller, J. S. ed.), Vol. 3, p. 43, New York-London, Plenum Press 1983
Journaux, Y., Kahn, O., Zarembowitch, J., Galy, J., Jaud, J.: J. Am. Chem. Soc. 105, 7585 (1983)
Carlin, R. L., Van Duyneveldt, A. J.: Magnetic Properties of Transition Metal Compounds, New York, Springer 1977
Lehninger, A. L.: The Mitrochondrion, New York, Benjamin 1973
Malström, B. G. in: Metal-Ion Activation of Dioxygen (Spiro, T. G. ed.), p. 181, New York, Wiley 1980
Cytochrome oxidase (King, T. E., Orii, Y., Chance, B., Okunuki, K. eds.), New York, Elsevier 1979
Palmer, G., Babcok, G. T., Vickery, L. E.: Proc. Natl. Acad. Sci. USA 73, 2206 (1976)
Babcock, G. T., Vickery, L. E., Palmer, G.: J. Biol. Chem. 253, 2400 (1978)
Tweedle, M. F., Wilson, L. J., Garcia-Iniguez, L., Babcock, G. T., Palmer, G.: ibid. 252, 8065 (1978)
Moss, T. H., Shapiro, E., King, T. E., Beinert, H., Hartzell, C. R.: ibid. 253, 8072 (1978)
Falk, K. E., Vänngard, T., Angström, J.: FEBS Lett. 75, 23 (1977)
Chance, B., Powers, L.: Biophys. J. 33, 95 (1981)
Powers, L., Chance, B., Ching, Y., Angiolillo, P.: ibid. 34, 465 (1981)
Powers, L., Chance, B.: J. Inorg. Biochem. 23, 207 (1985)
Scott, R. A., Schwartz, J. R., Cramer, S. P. in: Biological and Inorganic Copper Chemistry (Karlin, K. D., Zubieta, J. eds.), Vol. 1, p. 41, Guilderland, Adenine 1985
Reed, C. A., Landrum, J. T.: FEBS 106, 265 (1979)
Petty, R. H., Welch, B. R., Wilson, L. J., Bottomley, L. A., Kadish, K. M.: J. Am. Chem. Soc. 102, 611 (1980)
Berry, K. J., Clark, P. E., Gunter, M. J., Murray, K. S.: Nouv. J. Chim. 4, 581 (1980)
Gunter, M. J., Mander, L. N., McLaughlin, G. M., Murray, K. S., Berry, K. J., Clark, P. E., Bucklingham, D. A.: J. Am. Chem. Soc. 102, 1470 (1980)
Gunter, M. J., Mander, L. N., Murray, K. S., Clark, P. E.: ibid. 103, 6784 (1981)
Lukas, B., Miller, J. R., Silver, J., Wilson, M. T., Morrison, I. E. G.: J. Chem. Soc. Dalton 1035 (1982)
Elliott, C. M., Akabori, K.: J. Am. Chem. Soc. 104, 2671 (1982)
Desserts, S. E., Merrill, C. L., Saxton, R. J., Ilaria, Jr. R. L., Lindsey, J. W., Wilson, L. J.: ibid. 104, 4357 (1982)
Saxton, R. J., Wilson, L. J.: J. Chem. Soc. Chem. Commun. 359 (1984)
Petty, R. H., Wilson, L. J.: ibid. 483 (1978)
Okawa, H., Kanda, W., Kida, S.: Chem. Letters 1281 (1980)
Brewer, G. A., Sinn, E.: Inorg. Chem. 23, 2532 (1984)
Thomson, A. J., Johnson, M. K., Greenwood, C., Gooding, P. E.: Biochem. J. 193, 687 (1981)
Thomson, A. J., Greenwood, C., Gadsby, P. M. A., Peterson, J., Eglinton, D. G., Hill, B. C., Nicholls, P.: J. Inorg. Biochem. 23, 187 (1985)
Kent, T. A., Münck, E., Dunham, W. R., Filter, W. F., Findling, K. L., Yoshida, T., Fee, J. A.: J. Biol. Chem. 257, 2489 (1982)
Gunter, M. J., Berry, K. J., Murray, K. S.: J. Am. Chem. Soc. 106, 4227 (1984)
Okawa, H., Nishida, Y., Tanaka, M., Kida, S.: Bull. Chem. Soc. Jpn. 50, 127 (1977)
Torihara, N., Okawa, H., Kida, S.: Inorg. Chim. Acta 26, 97 (1976)
Morgenstern-Badarau, I., Rerat, M., Kahn, O., Jaud, J., Galy, J.: Inorg. Chem. 21, 3050 (1982)
Desjardins, S., Morgenstern-Badarau, I., Kahn, O.: ibid. 23, 3833 (1984)
Beale, J. P., Cunningham, J. A., Phillips, D. J.: Inorg. Chim. Acta 33, 113 (1979)
Tanaka, M., Kitaoka, M., Okawa, H., Kida, S.: Bull. Chem. Soc. Jprt. 49, 2469 (1976)
Mikuriya, M., Okawa, H., Kida, S., Ueda, I.: ibid. 51, 2920 (1978)
Lambert, S. L., Spiro, C. L., Gagne, R. R., Hendrickson, D. N.: Inorg. Chem. 21, 68 (1982)
Pilkington, N. H., Robson, R.: Aus. J. Chem. 23, 2225 (1970)
O'Connor, C. J., Freyberg, D. P., Sinn, E.: Inorg. Chem. 18, 1077 (1979)
Journaux, Y., Kahn, O., Morgenstern-Badarau, I., Galy, J., Jaud, J., Bencini, A., Gatteschi, D.: J. Am. Chem. Soc. 107, 6305 (1985)
Bencini, A., Gatteschi, D.: Mol. Phys. 54, 969 (1985)
Bencini, A., Caneschi, A., Dei, A., Gatteschi, D., Zanchini, C., Kahn, O.: Inorg. Chem. 25, 1374 (1986)
Kokoszka, G. F., Allen, Jr. H. C., Gordon, G.: J. Chem. Phys. 46, 3020 (1967)
Kokoszka, G. F., Duerst, R. W.: Coordin. Chem. Rev. 5, 209 (1970)
Banci, L., Bencini, A., Gatteschi, D., Dei, A.: Inorg. Chim. Acta 36, L419 (1979)
Banci, L., Bencini, A., Dei, A., Gatteschi, D.: Inorg. Chem. 20, 393 (1981)
Banci, L., Bencini, A., Benelli, C., Dei, A., Gatteschi, D.: ibid. 20, 1399 (1981)
Banci, L., Bencini, A., Benelli, C., Gatteschi, D.: ibid. 21, 3868 (1982)
Bencini A., Benelli C., Gatteschi, D., Zanchini, C.: J. Am. Chem. Soc. 102, 5820 (1980)
Krost, D. A., McPherson, G. L.: ibid. 100, 987 (1978)
Paulson, J. A., Krost, D. A., McPherson, G. L., Rogers, R. D., Atwood, J. L.: Inorg. Chem. 19, 2519 (1980)
McGarvey, B. R.: J. Phys. Chem. 71, 51 (1966)
Abragam, A., Bleaney, B.: Electron Paramagnetic Resonance of Transition Ions, New York, Clarendon Press 1970
Gagné, R. R., Spiro, C. L., Smith, T. J., Hamann, C. A., Thies, W. R., Shiemke, A. K.: J. Am. Chem. Soc. 103, 4073 (1981)
Eremin, M. V., Rakitin, Yu V.: Phys. Stat. Sol. b 80, 579 (1977); 82, 221 (1977); 85, 783 (1978)
Eremin, M. V., Kalinenkov, V. N., Rakitin, Yu V.: ibid. 89, 503 (1978); 90, 123 (1978)
Morgenstern-Badarau, I, Cocco, D., Desideri, A., Rotilio, G., Jordanov, J., Dupré, N.: J. Am. Chem. Soc. 108, 300 (1986)
Tainer, J. A., Getzoff, E. D., Beem, K. M., Richardson, J. S., Richardson, D. C.: J. Mol. Biol. 160, 181 (1982)
Valentine, J. S., Pantoliano, M. W. in: Copper Proteins (Spiro, T. G. ed.), p. 292, New York, Wiley Interscience 1982
Hartmann-Boutron, F.: J. Phys. Paris 29, 212 (1968)
Elliott, R. J., Thorpe, M. F.: J. Appl. Phys. 39, 802 (1968)
Levy, P. M.: Phys. Rev. 117, 509 (1969)
Lines, M. E.: J. Chem. Phys. 55, 2977 (1971)
Lines, M. E., Ginsberg, A. P., Martin, R. L., Sherwood, R. C.: J. Chem. Phys. 57, 1 (1972)
Barraclough, C. G., Gregson, A. K.: J. Chem. Soc. Faraday Trans. 11 177 (1972)
Kahn, O.: Mol. Phys. 29, 1039 (1975)
Stevens, K. W. H.: Phys. Rep. 24, 1 (1976)
Drillon, M., Georges, R.: Phys. Rev. B 24, 1278 (1981); 26, 3882 (1982)
Briat, B., Kahn, O., Morgenstern-Badarau, I.: Inorg. Chem. 20, 4193 (1981)
Fuchikami, N., Block, R.: Physica B + C 112, 369 (1982)
Kahn, O., Tola, P., Coudanne, H.: Chem. Phys. 42, 355 (1979)
Griffith, J. S.: The Theory of Transition Metal Ions, Cambridge, Cambridge University Press 1971
Bencini, A., Gatteschi, D., Zanchini, C.: Mol. Phys. 56, 97 (1985)
Taylor, C. P. S.: Biochim. Biophys. Acta 491, 137 (1977)
Palmer, G. in: The Porphyrins (Dolphin, D. ed.), Vol. 4, p. 313, New York, Academic Press 1979
Gruber, S. J., Harris, C. M., Sinn, E.: J. Chem. Phys. 49, 2183 (1968)
Gruber, S. J., Harris, C. M., Sinn, E.: J. Inorg. Nucl. Chem. 30, 1805 (1968)
Sinn, E. in: Biological and Inorganic Copper Chemistry (Karlin, K. D., Zubieta, J. eds.), Vol. 2, p. 195, Guilderland, Adenine 1985
Bencini, A., Benelli, C., Dei, A., Gatteschi, D.: Inorg. Chem. 24, 695 (1985)
Morgenstern-Badarau, I., Wickman, H. H.: ibid. 24, 1889 (1985)
Sekutowski, D., Jungst, R., Stucky, G. D.: ibid. 17, 1848 (1978)
Journaux, Y., Sletten, J., Kahn, O.: ibid. 25, 439 (1986)
Kahn, O.:Angew. Chem. Int. Ed. Engl. 24, 834 (1985)
Verdaguer, M., Julve, M., Gleizes, A., Kahn, O.:Nouv. J. Chim. 9, 325 (1985)
Bencini, A., Benelli, C., Caneschi, A., Carlin, R. L., Dei, A., Gatteschi, D.: J. Am. Chem. Soc. 107, 8128 (1985)
Bencini, A., Benelli, C., Caneschi, A., Dei, A., Gatteschi, D.: Inorg. Chem. 25, 572 (1986)
Ginsberg, A. P., Martin, R. L., Sherwood, R. C.: Inorg. Chem. 7, 932 (1968)
Pei, Y., Journaux, Y., Kahn, O., Dei, A., Gatteschi, D.: J. Chem. Soc. Chem. Comm. 1300 (1986)
Gleizes, A., Verdaguer, M.: J. Am. Chem. Soc. 103, 7373 (1981)
Verdaguer, M., Julve, M., Michalowicz, A., Kahn, O.: Inorg. Chem. 22, 2624 (1983)
Orbach, R.: Phys. Rev. 115, 1181 (1959)
Bonner, J. C., Fisher, M. E.: Phys. Rev. A 135, 640 (1964)
Drillon, M., Gianduzzo, J. C., Georges, R.: Phys. Lett. 96A, 413 (1983)
Coronado, E., Drillon, M., Beltran, D., Bernier, J. C.: Inorg. Chem. 23, 4000 (1984)
Georges, R., Curely, J., Drillon, M.: J. Appl. Phys. 58, 914 (1985)
Curely, J., Georges, R., Drillon, M.: Phys. Rev. B 33, 6243 (1986)
Drillon, M., Coronado, E., Beltran, D., Georges, R.: J. Appl. Phys. 57, 3353 (1984)
Drillon, M., Coronado, E., Beltran, D., Curely, J., Georges, R., Nugteren, P. R., De Jongh, L. J., Genicon, J. L.: J. Mag. Mag. Mater. 54–57, 1507 (1986)
Drillon, M., Coronado, E., Beltran, D., Georges, R.: Chem. Phys. 79, 449 (1983)
Fisher, M. E.: Am. J. Phys. 32, 241 (1974)
Seiden, J.: J. Phys. (Paris) Lett. 44, L947 (1983)
Verdaguer, M., Gleizes, A., Renard, J. P., Seiden, J.: Phys. Rev. B 29, 5144 (1984)
Gleizes, A., Verdaguer, M.: J. Am. Chem. Soc. 106, 3727 (1984)
Pei, Y., Sletten, J., Kahn, O.: ibid. 108, 3143 (1986)
Pei, Y., Verdaguer, M., Kahn, O., Sletten, J., Renard, J. P.: Inorg. Chem. 26, 138 (1987)
Pei, Y., Verdaguer, M., Kahn, O., Sletten, J., Renard, J. P.: J. Am. Chem. Soc. 108, 7428 (1986)
Pozhidaev, A. I., Polynova, T. N., Porai-Koshits, M. A., Neronova, N. N.: Zh. Strukt. Khim. 14, 570 (1973)
Coronado, E., Drillon, M., Fuertes, A., Beltran, D., Mosset, A., Galy, J.: J. Am. Chem. Soc. 108, 900 (1986)
Beltran, D., Escriva, E., Drillon, M.: J. Chem. Soc., Faraday Trans. 2, 78, 1773 (1982)
Seiden, J.: unpublished result
Peierls, R. E.: Quantum theory of Solids, London, Oxford Univ. Press 1955
Güdel, H. V. in: Magneto-Structural Correlations in Exchange Coupled Systems (Willett, R. D., Gatteschi, D., Kahn, O. eds.), p. 329, Dordrecht, D. Reidel 1985
Mathey, Y., Greig, D. R., Shriver, D. F.: Inorg. Chem. 21, 3409 (1982)
Daudey, J. P., De Loth, P., Malrieu, J. P. in: Magneto-Structural Correlations in Exchange Coupled Systems (Willett, R. D., Gatteschi, D., Kahn, O. eds.), p. 87, Dordrecht, D. Reidel 1985
De Loth, P., Cassoux, P., Daudey, J. P., Malrieu, J. P.: J. Am. Chem. Soc. 103, 4007 (1981)
Charlot, M. F., Verdaguer, M., Journaux, Y., De Loth, P., Daudey, J. P.: Inorg. Chem. 23, 3802 (1984)
Iwamura, H., Sugawara, T., Itoh, K., Takui, T.: Mol. Cryst. Liquid Cryst. 125, 251 (1985)
Sugawara, T., Bandow, S., Kimura, K., Iwamura, H., Itoh, K.: J. Am. Chem. Soc. 108, 368 (1986)
Author information
Authors and Affiliations
Rights and permissions
Copyright information
© 1987 Springer-Verlag
About this paper
Cite this paper
Kahn, O. (1987). Magnetism of the heteropolymetallic systems. In: Theoretical Approaches. Structure and Bonding, vol 68. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-18058-3_3
Download citation
DOI: https://doi.org/10.1007/3-540-18058-3_3
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-18058-6
Online ISBN: 978-3-540-47730-3
eBook Packages: Springer Book Archive