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Weak long-distance superexchange interaction and its temperature variations in copper(II) compounds studied by single crystal EPR

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Abstract

In this paper we review experimental EPR data and theoretical models of the weak super-exchange interaction (J<0.1 cm−1) mainly in copper(II) compounds single crystals. The different EPR techniques are described which allow one to determine the exchange coupling such weak asJ=0.0001 cm−1. Such a weak interaction is detectable by EPR on distances up to 25 Å and the presented data allowed us to establish empirical limits for a weak exchange coupling transmission forJ<0.3 cm−1 as |J lim|=5.9exp(−0.335R) whereR (Å) is the intermolecular distance. The weak superexchange coupling was found to be temperature dependent and this dependence is very specific to a crystal or molecular structure. In most cases temperature dependence of superexchange is governed by thermal crystal lattice contraction. A phenomenological model of competing potential and kinetic exchange is presented and used for description of copper(II) compounds with opposite temperature behaviour of superexchange coupling. Possible mechanisms driving temperature variations of superexchange are discussed.

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References

  1. Zavoisky E.K.: Sov. Phys.10, 197 (1946) (in Russian)

    Google Scholar 

  2. Bagguley D.M.S., Griffiths J.H.E.: Nature,162, 538 (1948); Bleaney B., Penrose P.P., Plumpton B.I.: Proc. Roy. Soc.198, 406 (1949)

    Article  ADS  Google Scholar 

  3. Hatfield W.E. in: Theory and Applications of Molecular Paramagnetism (Boundreaux E.A., Mulay L.N., eds.) chapter 7. New York: Willey 1976.

    Google Scholar 

  4. Furrer A., Gudel H.U.: J. Magn. Magn. Mater.14, 256 (1979)

    Article  ADS  Google Scholar 

  5. McCarthy P.J., Gudel H.U.: Inorg. Chem.,25, 838 (1986)

    Article  Google Scholar 

  6. Gudel H., Stebler A., Furrer A.: Inorg. Chem.,18, 1021 (1979)

    Article  Google Scholar 

  7. Carlin R.L.: Magnetochemistry. Berlin: Springer-Verlag 1986.

    Google Scholar 

  8. Galazka R.R., Nagata S., Keesom P.H.: Phys. Rev.,B22, 3344 (1980)

    ADS  Google Scholar 

  9. Lascaray J.P., Bruno A., Nawrocki M., Broto J.M., Ousset J.C., Askenazy S., Triboulet R.: Phys. Rev.B35, 6860 (1987)

    ADS  Google Scholar 

  10. Meier F., Bona G.L., Huefner S.: Phys. Rev. Lett.,52, 1152 (1984)

    Article  ADS  Google Scholar 

  11. Kirste B., Kruger A., Kurreck H.: J. Am. Chem. Soc.,104, 3850 (1982)

    Article  Google Scholar 

  12. Larsson S.: J. Chem. Soc. Faraday Trans.79, 1375 (1983)

    Article  Google Scholar 

  13. Todd M.D., Nitzan A., Ratner M.A.: J. Phys. Chem.,97, 29 (1993)

    Article  Google Scholar 

  14. Richardson P.F., Kreilick R.W.: J. Am. Chem. Soc.99, 8183 (1977)

    Article  Google Scholar 

  15. Hefni M.A., McConnell N.M., Rietmeijer F.J., Gribnau M.C.M., Keijzers C.P.: Mol. Phys.47, 1283 (1986).

    Article  ADS  Google Scholar 

  16. Hagiwara M., Katsumata K., Renard J.P.: J. Magn. Magn. Matter.90–91, 225 (1990)

    Google Scholar 

  17. Sreehari N., Manoharan P.T.: Mol. Phys.,63, 1077 (1988)

    Article  ADS  Google Scholar 

  18. Anderson P.W., Weiss P.R.: Rev. Mod. Phys.25, 269 (1953)

    Article  ADS  Google Scholar 

  19. Hoffmann S.K., Goslar J.: Acta Phys. Polon.A48, 707 (1975)

    Google Scholar 

  20. Kittel C., Abrahams E.: Phys. Rev.,90, 238 (1953)

    Article  ADS  Google Scholar 

  21. Więckowski A.B.: phys. status solidi,42, 125 (1970)

    Article  Google Scholar 

  22. Hoffmann S.K., Szczepaniak L.S., Szczepaniak E.: J. Magn. Reson.,70, 452 (1986)

    Google Scholar 

  23. Henderson A.J., Rogers R.N.: Phys. Rev.,152 218 (1966)

    Article  ADS  Google Scholar 

  24. Kubo R., Tomita K.J.: J. Phys. Soc. Japan9, 888 (1954)

    Article  ADS  Google Scholar 

  25. McGregor K.T., Soos Z.G.: J. Chem. Phys.64, 2506 (1976)

    Article  ADS  Google Scholar 

  26. Goslar J., Hilczer W., Hoffmann, S.K., Krupski M.: phys. status solidi (b)167, 291 (1991)

    Article  ADS  Google Scholar 

  27. Yokoi H., Ohsawa S.: Bull. Chem. Soc. Japan46, 2766 (1973)

    Article  Google Scholar 

  28. Ritter M.B., Drumheller J.E., Kite T.M., Snively L.O.: Phys. Rev.B28, 4949 (1983)

    Article  ADS  Google Scholar 

  29. Collison D., Gahan B., Mabb F.E.: J. Chem. Soc. Dalton Trans. 111 (1987)

  30. Steren C.A., Calvo R., Castellano E.E., Fabiane M.S., Piro O.E.: PhysicaB164, 323 (1990)

    Article  Google Scholar 

  31. Duggan D.M., Hendrickson D.N.: Inorg. Chem.13, 2929 (1974)

    Article  Google Scholar 

  32. Pierpout C.G., Francesconi L.C., Hendrickson D.N.: Inorg. Chem.116, 2367 (1977)

    Article  Google Scholar 

  33. Folgado J.V., Ibanez R., Coronado E., Beltran D., Savariault J.M., Galy J.: Inorg. Chem.27, 19 (1988)

    Article  Google Scholar 

  34. Costes J.P., Dahan F., Laurent J.P.: Inorg. Chem.31, 284 (1992)

    Article  Google Scholar 

  35. Takeuchi H., Tanaka H., Arakawa M.: J. Phys. Soc. Japan62, 2518 (1993)

    Article  ADS  Google Scholar 

  36. Byberg J.R., Bjerre N., Lund A., Samskog P.-O.: J. Chem. Phys.78, 5413 (1983)

    Article  ADS  Google Scholar 

  37. Eaton G.R., Eaton S.S.: Acad. Chem. Res.21, 107 (1988)

    Article  Google Scholar 

  38. Gahan B., Mabbs F.E.: J. Chem. Soc. Dalton 1695 (1983)

  39. Svare I., Seidel G.: Phys. Rev.A134, 172 (1964)

    Article  ADS  Google Scholar 

  40. Kuroda S.I., Motokawa M., Date M.: J. Phys. Soc. Japan61, 1036 (1992)

    Article  ADS  Google Scholar 

  41. Hoffmann S.K. in: Magnetic Resonance and Related Phenomena, 24th Congress AMPERE, Poznań, 1988 (Stankowski J., Piślewski N., Hoffmann S.K., Idziak S., eds.), pp. 373–385, Amsterdam: Elsevier 1989.

    Google Scholar 

  42. Bales B.P., Willett D.: J. Chem. Phys.80, 2997 (1984)

    Article  ADS  Google Scholar 

  43. Hughes R.C., Soos Z.G.: J. Chem. Phys.52, 6302 (1970)

    Article  ADS  Google Scholar 

  44. Hoffmann S.K.: Chem. Phys. Lett.98, 329 (1983)

    Article  ADS  Google Scholar 

  45. Hilczer W., Hoffmann S.K.: Chem. Phys. Lett.144, 199 (1988)

    Article  ADS  Google Scholar 

  46. Hoffmann S.K., Hilczer W.: Inorg. Chem.30, 2210 (1991)

    Article  Google Scholar 

  47. Hoffmann S.K., Goslar J., Szczepaniak L.S.: Phys. Rev.B37, 7331 (1988)

    Article  ADS  Google Scholar 

  48. Uschida Y., Isoya J., Weil J.A.: J. Phys. Chem.88, 5255 (1984)

    Article  Google Scholar 

  49. Schotland J., Leigh J.S.: J. Magn. Reson.51, 48 (1983)

    Google Scholar 

  50. Hoffmann S.K., Towle D.K., Hatfield W.E., Chaudhuri P., Weighardt K.: Inorg. Chem.24, 1307 (1985)

    Article  Google Scholar 

  51. Goslar J., Hilczer W., Hoffmann S.K., Strawiak M.M.: Ferroelectrics80, 3 (1988)

    Google Scholar 

  52. Kuppusamy P., Ramakrishna B.L., Manoharan P.T.: Proc. Indian Acad. Sci. (Chem. Sci.)93, 997 (1984)

    Google Scholar 

  53. Manoharan P.T., Noordik J.H., deBoer E., Keijzers C.P.: J. Chem. Phys.74, 1980 (1981)

    Article  ADS  Google Scholar 

  54. Hoffmann, S.K., Hodgson D.J., Hatfield W.E.: Inorg. Chem.24, 1194 (1985)

    Article  Google Scholar 

  55. Dyrek K., Goslar J., Hodorowicz S.A., Hoffmann S.K., Oleksyn B.J., Wesełucha-Birczyńska A.: Inorg. Chem.26, 1481 (1987)

    Article  Google Scholar 

  56. Goslar J., Hilczer W., Hoffmann S.K.: phys. status Solidi (b)175, 465 (1993)

    Article  ADS  Google Scholar 

  57. Balagopalakrishna C., Rajasekharan M.V.: Phys. Rev.B42, 7794 (1990)

    Article  ADS  Google Scholar 

  58. Balagopalakrishna C., Rajasekharan M.V., Bott S., Atwood J.L., Ramakrishna B.L.: Inorg. Chem.31, 2843 (1992)

    Article  Google Scholar 

  59. Hoffmann S.K., Gomółka-Marciniak M.: Solid State Commun.86, 63 (1993)

    Google Scholar 

  60. Hoffmann S.K., Goslar J., Hilczer W., Krupski M.: Inorg. Chem.32, 3554 (1993)

    Article  Google Scholar 

  61. Hoffmann S.K., Krupski M., Hilczer W.: Appl. Magn. Reson.5, 407 (1993)

    Article  Google Scholar 

  62. Bissey J.C., Beziade P., Servant Y.: J. Magn. Magn. Matter.127, 373 (1993)

    Article  ADS  Google Scholar 

  63. Bissey J.C., Beziade P., Servant Y.: Solid State Commun.89, 569 (1994)

    Article  ADS  Google Scholar 

  64. Servant Y., Bissey J.C., Maini M.: Physica106B, 343 (1981)

    Google Scholar 

  65. Borras-Almenar J.J., Coronado E., Gatteschi D., Gomez-Garcia C.J., Zanchini C.: J. Phys. Chem.97, 4206 (1993)

    Article  Google Scholar 

  66. Brondino C.D., Casado N.M.C., Passeggi M.C.G., Calvo R.: Inorg. Chem.32, 2078 (1993)

    Article  Google Scholar 

  67. Kramers H.A.: Physica1, 182 (1934)

    Article  MATH  ADS  Google Scholar 

  68. Anderson P.W.: Phys. Rev.115, 2 (1959); Solid State Phys.14, 99 (1963)

    Article  MATH  ADS  MathSciNet  Google Scholar 

  69. Hay P.J., Thibeault J.C., Hoffmann R.: J. Am. Chem. Soc.97, 4884 (1975)

    Article  Google Scholar 

  70. Kahn O., Briat B.: J. Chem. Soc. FaradayII 72, 268 and 1441 (1976)

    Google Scholar 

  71. Dance I.G.: Inorg. Chim. Acta9, 77 (1974)

    Article  Google Scholar 

  72. Bencini A., Gatteschi D.: Inorg. Chim. Acta31, 11 (1978)

    Article  Google Scholar 

  73. Harcourt R.D., Martin G.E.: J. Chem. Soc. Faraday273, 1 (1977)

    Article  Google Scholar 

  74. Eremin M.V., Rakitin Yu.V.: phys. stat. solidi (b)80, 579 (1977);82, 221 (1977)

    Article  ADS  Google Scholar 

  75. Kettle S.F.A., Tsaparlis G.R.: J. Chem. Phys.78, 5004 (1983)

    Article  ADS  Google Scholar 

  76. Jansen L., Block R.: Angew. Chem. Int. Eng. Ed.16, 294 (1977)

    Article  Google Scholar 

  77. Fuchikami N., Tanabe Y.: J. Phys. Soc. Japan45, 1559 (1978);47, 505 (1979)

    Article  ADS  Google Scholar 

  78. Fuchikami N., Bominaar E.L., Block R.: Physica150B, 185 (1988)

    Google Scholar 

  79. van Kalkeren G., Schmidt W.W., Block R.: Physica97B, 315 (1979)

    Google Scholar 

  80. Fuchikami N.: Physica115B, 219 (1983)

    Google Scholar 

  81. Yamaguchi K., Tsunekawa T., Toyoda Y., Fueno T.: Chem. Phys. Lett.143, 371 (1988)

    Article  ADS  Google Scholar 

  82. Hart J.R., Rappe A.K., Gorun S.M., Upton T.H.: J. Phys. Chem.96, 6255 (1992)

    Article  Google Scholar 

  83. de Loth P., Cassoux P., Daudey J.P., Malrieu J.P.: J. Am. Chem. Soc.103, 4007 (1981)

    Article  Google Scholar 

  84. de Loth P., Daudey J.P., Astheimer H., Walz L., Haase W.: J. Chem. Phys.82, 5048 (1985)

    Article  ADS  Google Scholar 

  85. Charlot M.F., Verdaguer M., Journaux Y., de Loth P., Daudey J.P.: Inorg. Chem.23, 3802 (1984)

    Article  Google Scholar 

  86. Broer R., Maaskant W.J.A.: Chem. Phys.102, 103 (1986)

    Article  Google Scholar 

  87. Miralles J., Daudey J.P., Caballo R.: Chem Phys. Lett.198, 131 (1986)

    Google Scholar 

  88. Noodleman L., Davidson E.R.: Chem. Phys.109, 131 (1986)

    Article  Google Scholar 

  89. Hart J.R., Rappe A.K., Gorun S.M., Upton T.H.: J. Phys. Chem.96, 6264 (1992)

    Article  Google Scholar 

  90. Fuchikami N.: Physica145B, 171 (1987)

    Google Scholar 

  91. Eremin M.V., Rakitin Yu.V.: J. Phys. C: Solid State Phys.15, L259 (1983)

    Article  Google Scholar 

  92. Mayer I., Angelov S.A.: J. Phys. C: Solid State Phys.16, L857 (1983)

    Article  ADS  Google Scholar 

  93. Anderson P.W. in: Solid State Physics (Seitz F., Turnball O., eds.), vol. 14, p. 99. New York: Academic Press 1963.

    Google Scholar 

  94. Rubenacker G.V., Haines D.N., Drumheller J.E., Emerson K.: J. Magn. Magn. Mater.43, 238 (1984)

    Article  ADS  Google Scholar 

  95. Blanchette J.J., Willett R.D.: Inorg. Chem.27, 843 (1988)

    Article  Google Scholar 

  96. Samuel E., Harrod J.F., Gourier D., Dromzee Y., Robert F., Jeannin Y.: Inorg. Chem.31, 3252 (1992)

    Article  Google Scholar 

  97. Bloch D.: J. Phys. Chem. Solids27, 881 (1966)

    Article  ADS  Google Scholar 

  98. Lowndes D.H., Finegold L., Rogers R.N.: Phys. Rev.186, 515 (1969)

    Article  ADS  Google Scholar 

  99. de Jongh L.J., Block R.: Physica79B, 568 (1975)

    Google Scholar 

  100. Groenendijk H.A., van Duyneveldt A.J., Willett R.D.: Physica98B, 53 (1979)

    Google Scholar 

  101. Coffman R.E., Buettner G.R.: J. Phys. Chem.83, 2387 (1979)

    Article  Google Scholar 

  102. Francesconi L.C., Corbin D.R., Clauss A.W., Hendrickson D.N., Stucky G.D.: Inorg. Chem.20, 2059 (1981)

    Article  Google Scholar 

  103. Aquino M.A.S., Lee F.L., Gabe E.J., Bensimon C., Greedan J.E., Crutchley R.J.: J. Am. Chem. Soc.114, 5130 (1992)

    Article  Google Scholar 

  104. Meredith D.J., Gill J.C.: Phys. Lett.25A, 429 (1967)

    ADS  Google Scholar 

  105. Kennedy T.A., Choh S.H., Seidel G.: Phys Rev. B2, 3645 (1970)

    Article  ADS  Google Scholar 

  106. Plumlee K.W., Hoffmann B.M., Ibers J.A., Soos Z.G.: J. Chem. Phys.63, 1926 (1972)

    Article  ADS  Google Scholar 

  107. Kamishina Y., Takada I., Kanda T.: J. Phys. Soc. Japan40, 1787 (1976)

    Article  ADS  Google Scholar 

  108. Simpson G.D., Belford R.L., Biaggioni R.: Inorg. Chem.17, 2424 (1978)

    Article  Google Scholar 

  109. Collins D., Gahan B., Mabbs F.E.: J. Chem. Soc. Dalton Trans.1983, 1705.

  110. Gatteschi D., Goslar J., Hilczer W., Hoffmann S.K., Zanchini C.: Inorg. Chem.28, 3395 (1989)

    Article  Google Scholar 

  111. Levstein P.R., Calvo R.: Inorg. Chem.29, 1581 (1990)

    Article  Google Scholar 

  112. Hoffmann S.K., Zimpel Z., Augustyniak M., Hilczer W., Szpakowska M.: J. Magn. Reson.98, 1 (1992)

    Google Scholar 

  113. Salikhov K.M., Tsvetkov Yu.D. in: Time Domain Electron Spin Resonance (Kevan L., Schwartz R.N., eds.), chp. 7, p. 247. New York: John Willey & Sons 1979.

    Google Scholar 

  114. Zaspel C.E., Drumheller J.E.: Phys. Rev.B16, 1771 (1977)

    Article  ADS  Google Scholar 

  115. Gavrilov V.V., Yablokov Yu.V., Milkova L.N., Ablov A.V.: phys. status solidi (b)45, 603 (1971)

    Article  ADS  Google Scholar 

  116. Kamishina Y., Takada I., Kanda T.: J. Phys. Soc. Japan40, 1787 (1976)

    Article  ADS  Google Scholar 

  117. Nakatsuka S., Osaki K., Uryu N.: Inorg. Chem.21, 4332 (1982)

    Article  Google Scholar 

  118. Kahn O., Morgenstern-Badarau I., Audiere J.P., Lehn J.M., Sullivan S.A.: J. Am. Chem. Soc.102, 5935 (1980)

    Article  Google Scholar 

  119. Oberhausen K.J., Richardson J.F., O’Brien R.J., Buchanan R.M., McCusker J.K., Webb R.J., Hendrickson D.N.: Inorg. Chem.31, 1123 (1992)

    Article  Google Scholar 

  120. Hilczer W., Goslar J., Tritt-Goc J., Hoffmann S.K.: Inorg. Chem. (submitted for publication)

  121. Hoffmann S.K., Waśkowska A., Hilczer W.: Solid State Commun.74, 1359 (1990)

    Article  ADS  Google Scholar 

  122. Alvarez S., Julve M., Verdaguer M.: Inorg. Chem.29, 4500 (1990)

    Article  Google Scholar 

  123. Astheimer H., Haase W.: J. Chem. Phys.85, 1427 (1988)

    Article  ADS  Google Scholar 

  124. Handa M., Koga N., Kida S.: Bull. Chem. Soc. Japan61, 3853 (1988)

    Article  Google Scholar 

  125. Reibenspies J.H., Anderson O.P., Eaton S.S., More K.M., Eaton G.R.: Inorg. Chem.26, 132 (1987)

    Article  Google Scholar 

  126. Alster E., Silver B.L.: Mol. Phys.58, 977 (1986)

    Article  ADS  Google Scholar 

  127. McGregor K.T., Soos Z.: Inorg. Chem.15, 2159 (1976)

    Article  Google Scholar 

  128. Graja A., Sekretarczyk G., Krupski M.: J. Physique46, 1743 (1985)

    Article  Google Scholar 

  129. Beswick J., Dugdale D.E.: J. Phys. C: Solid State Phys.6, 3326 (1973)

    Article  ADS  Google Scholar 

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  1. Institute of Molecular Physics, Polish Academy of Sciences, Smoluchowskiego 17, PL-60179, Poznan, Poland

    S. K. Hoffmann, W. Hilczer & J. Goslar

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  1. S. K. Hoffmann
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Hoffmann, S.K., Hilczer, W. & Goslar, J. Weak long-distance superexchange interaction and its temperature variations in copper(II) compounds studied by single crystal EPR. Appl. Magn. Reson. 7, 289–321 (1994). https://doi.org/10.1007/BF03162617

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