H. He et al. / Inorganica Chimica Acta 378 (2011) 30–35
35
Table 3
red-shift is observed for nickel compound. The theoretical calcula-
tion reveals that red-shift in the free base comes from significant
lowering of LUMO energy level.
Major transition of two chlorinated porphyrins and their oscillation strength (f).
Porphyrin Transition
TCl12PPH 668.2
f
Compositions (percentage)
Character
Singlet
2
0.1328 HOMOÀ1 ? LUMO+1 (19%)
HOMO ? LUMO (80%)
Acknowledgements
6
4
16.6
63.2
0.1552 HOMOÀ1 ? LUMO (25%)
Singlet
Singlet
HOMO ? LUMO+1 (75%)
This material is based upon work supported by the National Sci-
ence Foundation/EPSCoR (0903804), the State of South Dakota, and
Ph.D. program in the Department of Electrical Engineering and
Computer Science, SDSU, and South Dakota State University
Administration & Research Computing.
0.7018 HOMOÀ3 ? LUMO (25%),
HOMOÀ1 ? LUMO+1 (59%)
HOMO ? LUMO (11%)
4
4
3
51.9
32.4
70.3
1.5201 HOMOÀ1 ? LUMO (72%)
Singlet
Singlet
Singlet
Singlet
HOMO ? LUMO+1 (À24%)
0.8105 HOMOÀ3 ? LUMO (72%)
HOMOÀ1 ? LUMO+1 (16%)
0.1638 HOMOÀ8 ? LUMO (76%)
HOMOÀ7 ? LUMO (21%)
Appendix A. Supplementary material
TCl12PPNi 562.9
0.0181 HOMOÀ1 ? LUMO (19%)
HOMOÀ1 ? LUMO+1 (23%)
HOMO ? LUMO (32%),
CCDC 812564 and 812565 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
HOMO ? LUMO+1 (À26%)
4
4
3
45.2
26.4
86.6
1.3008 HOMOÀ1 ? LUMO (54%)
HOMO ? LUMO+1 (38%)
Singlet
Singlet
Singlet
0.0809 HOMOÀ9 ? LUMO (À43%)
HOMOÀ4 ? LUMO (52%)
0.0629 HOMOÀ9 ? LUMO (48%)
HOMOÀ5 ? LUMO+1 (À10%)
HOMOÀ4 ? LUMO (35%)
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The time-depended DFT (TD-DFT) calculations were also carried
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The assignments of those peaks and their corresponding oscillation
strengths are listed in Table 3, which still can be explained by Gou-
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due to the structure distortion. This model includes two highest
occupied orbitals (HOMO and HOMOÀ1) and two lowest unoccu-
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tier orbitals of chlorinated porphyrin are degenerated and gap
between orbitals narrowed. As a result, the absorption is red-
shifted. More pronounced effect is observed in free base then in
nickel compound.
[
[
[
4
. Conclusion
The chlorination of eight b-pyrrolic position of porphyrin leads to
the distortion of ring structure, resulting saddled conformations.
The distortion is more pronounced in free base than in nickel com-
pound. The introductionof additionalfour chlorineatoms in the para
position of phenyl group does not exert obvious impact on the
porphyrin structure. After chlorination the optical onset red-shifts
to the near-infrared region for free base; however, no significant
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4