Structure and Properties of Perfluoroalkylated Phthalocyanines. A Theoretical Study

Authors

M.-S. Liao
J. D. Watts
S. M. Gorun
Steve Scheiner, Utah State UniversityFollow
M.-J. Huang

Document Type

Article

Journal/Book Title

Journal of Theoretical and Computational Chemistry

Publication Date

3-2008

Publisher

World Scientific Publishing

Volume

7

Issue

4

First Page

541

Last Page

563

Abstract

Density functional theory (DFT) calculations are performed on a series of peripherally substituted free-base and fluorinated zinc phthalocyanines, namely F_nPcM (M = 2H, Zn; n = 16, 32, 48, 64). F₁₆PcM, F₃₂PcM, and F₄₈PcM all prefer a planar skeletal structure of the metallomacrocycle core. In the case of F₆₄Pc, F₆₄PcZn remains planar but F₆₄PcH₂ is domed. The occurrence of a dome distortion appears to be related, at least in part, to the orientation of the isopropyl -C₃F₇ substituents as well as to the intermolecular (packing) interactions. The trends in the calculated results of the Pc^2-–M²⁺ binding energy, polarizabilities, and electron excitation energies in H₁₆PcM, F₁₆PcM, and F₆₄PcM are in agreement with the experimental observations, as are the geometrical features. It is further confirmed that the simpler F₃₂PcM or F₄₈PcM mimic the basic electronic properties of F₆₄PcM.

Comments

http://www.worldscinet.com/jtcc/07/0704/S0219633608003952.html

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Published by World Scientific Publishing in Journal of Theoretical and Computational Chemistry.

Recommended Citation

Structure and Properties of Perfluoroalkylated Phthalocyanines. A Theoretical Study M.S. Liao, J. D. Watts, S. M. Gorun, S. Scheiner, M.-J. Huang J. Theor. Comput. Chem. 2008 7 541-563