Synthesis, crystal structure, molecular orbital calculations and electronic properties of 2,3-di(2-pyridyl)naphtho[2,3-f  ]quinoxaline-7,12-quinone (Aqdpp)

Abstract

The synthesis, characterization and crystal structure of 2,3-di(2-pyridyl)naphtho[2,3-f  ]quinoxaline-7,12-quinone (Aqdpp) are reported. Molecular orbital calculations have been carried out in order to characterize its reactivity and coordination properties. Surface maps for the electronegativity, hardness and Fukui functions have been generated to identify local reactivity sites and the crystal structure has been compared with the optimized geometry with good correlation among them. The acceptor properties of the Aqdpp ligand are shown by the orbital map for the LUMO level contributed mainly by the quinonic region of the ligand.

References

1. (a) T. J. Meyer, Acc. Chem. Res., 1989, 22, 163; (b) T. J. Meyer, in Photochemical Processes in Organized Molecular Systems, ed. K. Honda, Elsevier, Amsterdam, 1991, p. 133.
2. (a) G. Tapolsky, R. Duesing and T. J. Meyer, Inorg. Chem., 1990, 29, 2285; (b) J. P. Sauvage, J. P. Collin, J. C. Chambron, S. Guillerez, C. Coundret, V. Balzani, F. Barigelleti, L. Della and L. Falmigni, Chem. Rev., 1994, 94, 993; (c) W. Lynne and P. Rillema, Inorg. Chem., 1993, 32, 3836.
3. R. López, B. Loeb, T. Boussie and T. J. Meyer, Tetrahedron Lett., 1996, 37, 5437.
4. R. G. Parr and W. Yang, Density Functional Theory of Atoms and Molecules, Oxford University Press, New York, 1989.
5. G. Liu and R. G. Parr, J. Am. Chem. Soc., 1995, 117, 3179 and references therein.
6. G. M. Sheldrick, SHELXTL-Plus, release 4.2 for Siemens Crystallographic Research System, Siemens Analytical X-ray Ray Instruments, Inc., Madison, Wisconsin, USA, 1990.
7. C. Lee, W. Yang and R. G. Parr, Phys. Rev., Sect. B, 1988, 37, 785.
8. SPARTAN, version 4.1, Wavefunction Inc., Von Karman Ave. 370, 18401 Irvine, CA, 1996.
9. A. D. Becke, Phys. Rev., Sect. A, 1988, 38, 3089.
10. P. Sjoberg and P. Politzer, J. Phys. Chem., 1990, 94, 3959.
11. (a) P. Politzer, R. G. Parr and D. R. Murphy, J. Chem. Phys., 1983, 79, 3859; (b) M. K. Harbola, R. G. Parr and C. Lee, J. Chem. Phys., 1991, 94, 6055.
12. R. G. Pearson, J. Org. Chem., 1989, 96, 3283; R. G. Pearson and W. E. Palke, J. Phys. Chem., 1992, 96, 3283; R. G. Pearson, Acc. Chem. Res., 1993, 26, 250.
13. M. K. Harbola, Proc. Natl. Acad. Sci. USA, 1992, 89, 1036.
14. Z. Zhou and R. G. Parr, J. Am. Chem. Soc., 1990, 112, 5722.
15. F. Zuloaga, R. Tapia and C. Quintanar, J. Chem. Soc., Perkin Trans. 2, 1995, 939.
16. M. Berkowitz and R. G. Parr, J. Chem. Phys., 1988, 88, 2554.
17. K. Fukui, Science, 1987, 218, 747.
18. W. Yang, R. G. Parr and R. Pucci, J. Chem. Phys., 1984, 81, 2862.
19. Absorption Spectra in the Ultraviolet and Visible Region, ed. L. Lang, Academic Press, New York, 1967, vol. 8.
20. E. Norambuena, R. López and B. Loeb, unpublished work.
21. P. Politzer and H. Weinstein, J. Chem. Phys., 1979, 71, 4218.
22. B. J. Yoblinski, M. Stathis and T. F. Guarr, Inorg. Chem., 1992, 31, 5.
23. A. M. Leiva, R. López and B. Loeb, unpublished results.