MCD spectroscopy and TD-DFT calculations of low symmetry subnaphthalocyanine analogs
John Mack1, Tatsuya Otaki2, William S Durfee3
1Department of Chemistry, Rhodes University, Grahamstown 6140, South Africa; Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan; Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada.
Abstract:
Magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations are used to analyze the electronic structure and optical properties of low-symmetry subnaphthalocyanine analogs with AAB and ABB structures formed during mixed condensations of tetrafluorophthalonitrile and 2,3-naphthalenedicarbonitrile. The results demonstrate that trends observed in the properties of phthalocyanine analogs can be used to fine tune the optical properties so that the Q(0,0) bands lie in the red region, in a manner that does not significantly destabilize the highest occupied molecular orbital (HOMO) energy relative to that of the parent subphthalocyanine ligand. Attempts to study the spectroscopy of anion radical species proved unsuccessful, since they proved to be unstable.
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