Experimentally Validated Model for the Prediction of the HOMO and LUMO Energy Levels of Boronsubphthalocyanines

We report the rapid screening of phenoxyboronsubphthalocyanine (PhO-BsubPc) derivatives for sensitivity of their HOMO and LUMO energy levels (E H and E L) to substitution with electron-donating and electron-withdrawing functional groups using semiempirical methods. Subsequently, we have synthesized...

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Veröffentlicht in:Journal of physical chemistry. C 2011-06, Vol.115 (23), p.11709-11718
Hauptverfasser: Morse, Graham E, Helander, Michael G, Stanwick, Jason, Sauks, Jennifer M, Paton, Andrew S, Lu, Zheng-Hong, Bender, Timothy P
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Sprache:eng
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Zusammenfassung:We report the rapid screening of phenoxyboronsubphthalocyanine (PhO-BsubPc) derivatives for sensitivity of their HOMO and LUMO energy levels (E H and E L) to substitution with electron-donating and electron-withdrawing functional groups using semiempirical methods. Subsequently, we have synthesized a selection of seven PhO-BsubPc derivatives, further modeled the seven derivatives using DFT methods, and measured or determined their respective E H and E L. We have used a combination of ultraviolet photoelectron spectroscopy (UPS), cyclic voltammetry (CV), and ultraviolet–visible (UV–vis) spectroscopy to correlate the computational predictions with experimental data. From these experimental and computational results, we have shown that E H and E L of PhO-BsubPcs are more sensitive to peripheral substitutions than to substitution on the axial phenoxylate. The frontier molecular orbitals, calculated using DFT methods, were found to be exclusively located on the boronsubphthalocyanine ligand among the seven PhO-BsubPc derivatives. A mathematical model correlating computational results with experimental data was determined which can be subsequently used to rapidly predict how structural factors influence the E H and E L to direct synthetic and engineering efforts.
ISSN:1932-7447
1932-7455
DOI:10.1021/jp1092306