Hostname: page-component-586b7cd67f-gb8f7 Total loading time: 0 Render date: 2024-11-25T17:41:15.118Z Has data issue: false hasContentIssue false
  • English
  • Français

Ligand Substitution Effect on Optical Properties in Conducting Tetraazaporphyrines

Published online by Cambridge University Press:  15 February 2011

Liqun Guo ,
D. E. Ellis ,
O. V. Gubanova  and
B. M. Hoffman
Liqun Guo
Affiliation:
Materials Research Center, Northwestern University, Evanston, IL 60208
D. E. Ellis
Affiliation:
Materials Research Center, Northwestern University, Evanston, IL 60208
O. V. Gubanova
Affiliation:
Materials Research Center, Northwestern University, Evanston, IL 60208
B. M. Hoffman
Affiliation:
Materials Research Center, Northwestern University, Evanston, IL 60208
Get access

Abstract

Self-consistent Density Functional calculations have been performed on a variety of planar conjugated Ni-centered macrocycles with a basic tetraazaporphyrinic core and dithiolene groups (PZ) or fused-benzo groups (PC). Theoretical energy diagrams, charge and spin distributions and densities of states have been obtained in order to understand the electronic structure modifications due to peripheral ligand substitution. The substituents role in altering electronic properties and charge distribution of the porphyrazine macrocycles has been used to interpret the observed variations in optical absorption profiles. In the Q-band (∼ 680 nm) region, a single peak is seen for high symmetry (D4h) macrocycles and a double peak for lower symmetry (D2h and C2v) systems. Calculated intensities and band splittings are compared in detail with qualitative molecular orbital models and experiment in the visible and UV regions. Predictions are made for the infrared absorption and semiconducting band gap.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 393: Symposium W – Materials for Electrochemical Energy Storage and Conversion , 1995 , 137
Copyright
Copyright © Materials Research Society 1995

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

References:

1 Liang, X. L., Flores, S., Ellis, D. E., Hoffman, B. M.,and Musselman, R. L., J.Chem.Phys. 95, 40 (1991) and references therein.Google Scholar
2 Liang, X. L., Ellis, D. E., Gubanova, O. V.,and Hoffman, B. M., Int. J. of Quan. Chem. 52, 657 (1994)Google Scholar
3 Yuichi, Ishikawa, private communicationGoogle Scholar
4 Ellis, D. E. and Painter, G. S., Phys. Rev. B, 2, 2887 (1970)Google Scholar
5 Delley, B. and Ellis, D. E., J. Chem. Phys. 76, 1949 (1982)Google Scholar
6 Velazquez, C., Hoffman, B. M.et al, J. Am. Chem. Soc., 114 , 7416 (1992)Google Scholar