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Preparation, characterization and crystal structures of copper(II) hexaazamacrotetracyclic complexes with organic ligands

Abstract

The reaction of [Cu(L)](ClO4)2 · H2O (L=1,3,10,12,16,19-hexaazatetracyclo[17,3,1,112.16,04.9]tetracosane) with NaN3 and Na2tp yields mononuclear and dinuclear copper(II) complexes, [Cu(L)(N3)](ClO4) (1) and [Cu(L)(μ-tp)](ClO4) · 2H2O (2). These complexes have been characterized by X-ray crystallography, electronic absorption, cyclic voltammetry and magnetic susceptibility. The crystal structure of (1) shows that the copper(II) ion has a distorted square-pyramidal geometry with the two secondary and two tertiary amines of the macrocycle and one nitrogen atom from the azide group coordinating the axial position. The copper(II) ions in (2) are bridged by the terephthalate anion to form a dinuclear complex, in which each copper(II) ion reveals a distorted square-pyramid with four nitrogen atoms of the macrocycle and the oxygen atom of bridging tp ligand. Cyclic voltammetry of the complexes gives two one-electron waves corresponding to CuII/CuIII and CuII/CuI processes. The magnetic susceptibility measurement for (2) exhibits a weak antiferromagnetic interaction between copper(II) centers with a 2J value of −2.21 cm−1 (H = −2JΣS1 · S2). The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the organic ligands.

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References

  1. M.K. Beklemishev S. Elshani C.M. Wai (1994) Anal. Chem. 66 3521 Occurrence Handle10.1021/ac00092a036

  2. B.S. Mohite D.N. Zambare B.E. Mahadik (1994) Anal. Chem. 66 4097 Occurrence Handle10.1021/ac00094a037

  3. J.F. Carvalho S.H. Kim C.A. Chang (1992) Inorg. Chem. 31 4065 Occurrence Handle10.1021/ic00046a015

  4. K.D. Karlin Z. Tyeklar (1991) Bioinorganic Chemistry of Copper Chapman and Hall New York

  5. D.E. Fenton and H. Okawa, J. Chem. Soc., Dalton Trans., 1349 (1993).

  6. E. Kimura, C.A. Dalimunte, A. Yamashita and R. Machida, J. Chem. Soc., Chem. Commun., 1041 (1985).

  7. C. Tu D.N. Silverman (1989) Biochemistry 28 7913 Occurrence Handle10.1021/bi00445a054 Occurrence Handle2514797

  8. K.M. Merz J.R. Hoffmann M.J.S. Dewar (1989) J. Am. Chem. Soc. 111 5637

  9. K. Kumar C.A. Chang M.F. Tweedle (1993) Inorg. Chem. 32 587 Occurrence Handle10.1021/ic00057a017

  10. J.M. Lehn J.P. Sauvage (1975) J. Am. Chem. Soc. 97 6700 Occurrence Handle10.1021/ja00856a018

  11. K. Kumar M.F. Tweedle (1993) Inorg. Chem. 32 4193 Occurrence Handle10.1021/ic00072a008

  12. K.-Y. Choi H. Ryu I.-H. Suh (1998) Polyhedron 17 1241 Occurrence Handle10.1016/S0277-5387(97)00393-8

  13. K.-Y. Choi Y.-J. Kim H. Ryu I.-H. Suh (1999) Inorg. Chem. Commun. 2 176 Occurrence Handle10.1016/S1387-7003(99)00041-6

  14. K.-Y. Choi, M.R. Oh and I.-H. Suh, Chem Lett., 141 (1997).

  15. K.-Y. Choi (1998) J. Chem. Crystallogr. 28 875 Occurrence Handle10.1023/A:1022894318159

  16. K.-Y. Choi (2002) J. Incl. Phenom. Macrocyc. Chem. 43 195 Occurrence Handle10.1023/A:1021236700141

  17. J.C. Kim J. Cho A.J. Lough (2001) Inorg. Chim. Acta 317 252 Occurrence Handle10.1016/S0020-1693(01)00426-1

  18. E.G. Bakalbassis P. Bergerat O. Kahn S. Jeannin Y. Jeannin Y. Dromzee M. Guillot (1992) Inorg. Chem. 31 625 Occurrence Handle10.1021/ic00030a019

  19. E.G. Bakalbassis J. Mrozinski C.A. Tsipis (1986) Inorg. Chem. 25 3684 Occurrence Handle10.1021/ic00240a033

  20. J. Cano, G. DeMunno, J.L. Sanz, R. Ruiz, J. Faus, F. Lloret, M. Julve and A. Caneschi, J. Chem. Soc., Dalton Trans., 1915 (1997).

  21. M. Verdaguer J. Gouteron S. Jeannin Y. Jeannin O. Kahn (1984) Inorg. Chem. 23 4291 Occurrence Handle10.1021/ic00193a038

  22. L. Deakin A.M. Arif J.S. Miller (1999) Inorg. Chem. 38 5072 Occurrence Handle11671253

  23. S.-G. Kang S.-K. Jung (1991) J. Kor. Chem. Soc. 35 527

  24. G.M. Sheldrick (1990) Acta Crystallogr., Sect. A 46 467

  25. G.M. Sheldrick (1997) SHELXL-97, Program for the Refinement of Crystal Structures University of Göttingen Germany

  26. R.R. Holmes (1984) J. Am. Chem. Soc. 106 3745 Occurrence Handle10.1021/ja00325a006

  27. M.P. Suh S.-G. Kang V.L. Goedken S.-H. Park (1991) Inorg. Chem. 30 365 Occurrence Handle10.1021/ic00003a004

  28. M.P. Suh W. Shin S.-G. Kang M.S. Lah T.-M. Chung (1989) Inorg. Chem. 28 1602 Occurrence Handle10.1021/ic00307a036

  29. S.-G. Kang K. Ryu M.P. Suh J.H. Jeong (1997) Inorg. Chem. 36 2478 Occurrence Handle10.1021/ic961419m Occurrence Handle11669893

  30. K.-Y. Choi H. Ryu I.-H. Suh (2000) Inorg. Chim. Acta 299 268 Occurrence Handle10.1016/S0020-1693(99)00492-2

  31. B.J. Hathaway (1991) Structure and Bonding (Berlin) 57 2801

  32. S.-G. Kang S.-J. Kim K. Ryu J. Kim (1998) Inorg. Chim. Acta 274 24 Occurrence Handle10.1016/S0020-1693(97)05986-0

  33. D.O. Nielson M.L. Larsen R.D. Willett J.I. Legg (1971) J. Am. Chem. Soc. 93 5079 Occurrence Handle10.1021/ja00749a020

  34. B. Bleaney K.D. Bowers (1952) Proc. R. Soc., London, Ser. A 214 451

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Correspondence to Ki-Young Choi.

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Choi, K., Kim, M. & Kim, M. Preparation, characterization and crystal structures of copper(II) hexaazamacrotetracyclic complexes with organic ligands. Transition Met Chem 29, 904–910 (2004). https://doi.org/10.1007/s11243-004-2436-1

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Keywords

  • Nitrogen Atom
  • Magnetic Susceptibility
  • Cyclic Voltammetry
  • Terephthalate
  • Macrocycle