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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
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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

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References

References:

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