Electronic structure and bonding in metal phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg
10.1063/1.1367374
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

Electronic structure and bonding in metal phthalocyanines (Metal=Fe, Co, Ni, Cu, Zn, Mg) is investigated in detail using a density functional method. The metal atoms are strongly bound to the phthalocyanine ring in each case, by as much as 10 eV. The calculated orbital energy levels and relative total energies of these D4h structures indicate that Fe and Co phthalocyanines have A2g3 and Eg2 ground states, respectively, but that these states are changed upon interaction with strong-field axial ligands. The valence electronic structures of Fe and Co phthalocyanines differ significantly from those of the others. The HOMOs in Fe, Co, and Cu phthalocyanine are metal 3d-like, whereas in Ni and Zn phthalocyanines, the HOMO is localized on the phthalocyanine ring. The first ionization removes an electron from the phthalocyanine a1u orbital in all cases, with very little sensitivity of the ionization energy to the identity of the metal. Whereas the first reduction in Fe and Co phthalocyanine occurs at the metal, it is the phthalocyanine that is reduced upon addition of an electron to the other systems. Fe, Ni, and Cu phthalocyanines have smaller HOMO–LUMO separations than do Zn and Co phthalocyanine. There is very little variation in atomic charges within the phthalocyanine from one metal to the next.

Bibliography

Liao, M.-S., & Scheiner, S. (2001). Electronic structure and bonding in metal phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg. The Journal of Chemical Physics, 114(22), 9780–9791.

Authors 2
  1. Meng-Sheng Liao (first)
  2. Steve Scheiner (additional)
References 51 Referenced 563
  1. 10.1351/pac198658111467 / Pure Appl. Chem. (1986)
  2. 10.1021/ja00048a046 / J. Am. Chem. Soc. (1992)
  3. 10.1021/cr980439y / Chem. Rev. (1999)
  4. {'key': '2024020519274456000_r4'}
  5. 10.1007/BF01046366 / Theor. Chim. Acta (1972)
  6. 10.1007/BF00868856 / Theor. Chim. Acta (1972)
  7. 10.1080/00268977100101601 / Mol. Phys. (1971)
  8. 10.1002/qua.560060105 / Int. J. Quantum Chem. (1972)
  9. 10.1007/BF01007552 / Theor. Chim. Acta (1972)
  10. 10.1016/S0020-1693(00)90928-9 / Inorg. Chim. Acta (1977)
  11. 10.1021/j100217a009 / J. Phys. Chem. (1982)
  12. 10.1063/1.450586 / J. Chem. Phys. (1986)
  13. 10.1063/1.455251 / J. Chem. Phys. (1988)
  14. 10.1021/ja00084a038 / J. Am. Chem. Soc. (1994)
  15. 10.1016/S0166-1280(98)00238-3 / J. Mol. Struct.: THEOCHEM (1998)
  16. {'key': '2024020519274456000_r15'}
  17. 10.1016/0042-207X(94)00107-3 / Vacuum (1995)
  18. 10.1021/ja00413a003 / J. Am. Chem. Soc. (1981)
  19. 10.1021/ic00206a040 / Inorg. Chem. (1985)
  20. {'key': '2024020519274456000_r19'}
  21. 10.1063/1.464906 / J. Chem. Phys. (1993)
  22. 10.1021/ic50114a003 / Inorg. Chem. (1972)
  23. 10.1021/ic50183a011 / Inorg. Chem. (1978)
  24. 10.1063/1.1674237 / J. Chem. Phys. (1970)
  25. 10.1039/f29747000790 / J. Chem. Soc., Faraday Trans. 2 (1974)
  26. {'key': '2024020519274456000_r25'}
  27. 10.1246/bcsj.69.2111 / Bull. Chem. Soc. Jpn. (1996)
  28. 10.1246/bcsj.69.245 / Bull. Chem. Soc. Jpn. (1996)
  29. {'key': '2024020519274456000_r26b', 'first-page': '1299', 'volume-title': 'Chem. Lett.', 'year': '1993'} / Chem. Lett. (1993)
  30. 10.1016/0022-1902(61)80142-5 / J. Inorg. Nucl. Chem. (1961)
  31. 10.1063/1.457915 / J. Chem. Phys. (1990)
  32. 10.1016/0301-0104(73)80059-X / Chem. Phys. (1973)
  33. 10.1016/0021-9991(92)90277-6 / J. Comput. Phys. (1992)
  34. 10.1021/j100345a036 / J. Phys. Chem. (1989)
  35. 10.1007/BF02401406 / Theor. Chim. Acta (1977)
  36. 10.1139/p80-159 / Can. J. Phys. (1980)
  37. 10.1103/PhysRevA.38.3098 / Phys. Rev. A (1988)
  38. 10.1103/PhysRevB.33.8800 / Phys. Rev. B (1986)
  39. 10.1021/ja00278a010 / J. Am. Chem. Soc. (1986)
  40. 10.1021/ic50161a042 / Inorg. Chem. (1976)
  41. {'key': '2024020519274456000_r37'}
  42. {'key': '2024020519274456000_r38'}
  43. {'key': '2024020519274456000_r39'}
  44. 10.1021/ja00446a021 / J. Am. Chem. Soc. (1977)
  45. 10.1002/zaac.19966220625 / Allg. Chem. (1996)
  46. 10.1063/1.479584 / J. Chem. Phys. (1999)
  47. {'key': '2024020519274456000_r43'}
  48. 10.1063/1.437867 / J. Chem. Phys. (1979)
  49. 10.1021/ja00797a008 / J. Am. Chem. Soc. (1973)
  50. 10.1021/ja00713a010 / J. Am. Chem. Soc. (1970)
  51. 10.1016/0022-2852(70)90050-0 / J. Mol. Spectrosc. (1970)
Dates
Type When
Created 23 years, 1 month ago (July 26, 2002, 10:17 a.m.)
Deposited 1 year, 6 months ago (Feb. 5, 2024, 3:33 p.m.)
Indexed 3 weeks, 4 days ago (Aug. 7, 2025, 4:47 p.m.)
Issued 24 years, 2 months ago (June 8, 2001)
Published 24 years, 2 months ago (June 8, 2001)
Published Print 24 years, 2 months ago (June 8, 2001)
Funders 0

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@article{Liao_2001, title={Electronic structure and bonding in metal phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg}, volume={114}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1367374}, DOI={10.1063/1.1367374}, number={22}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Liao, Meng-Sheng and Scheiner, Steve}, year={2001}, month=jun, pages={9780–9791} }