Experimentally Validated Model for the Prediction of the HOMO and LUMO Energy Levels of Boronsubphthalocyanines
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- 作者：Graham E. Morse ; Michael G. Helander ; Jason Stanwick ; Jennifer M. Sauks ; Andrew S. Paton ; Zheng-Hong Lu ; Timothy P. Bender
- 刊名：Journal of Physical Chemistry C
- 出版年：2011
- 出版时间：June 16, 2011
- 年：2011
- 卷：115
- 期：23
- 页码：11709-11718
- 全文大小：1048K
- 年卷期：v.115,no.23(June 16, 2011)
- ISSN：1932-7455
文摘
We report the rapid screening of phenoxyboronsubphthalocyanine (PhO-BsubPc) derivatives for sensitivity of their HOMO and LUMO energy levels (EH and EL) 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 EH and EL. We have used a combination of ultraviolet photoelectron spectroscopy (UPS), cyclic voltammetry (CV), and ultraviolet鈥搗isible (UV鈥搗is) spectroscopy to correlate the computational predictions with experimental data. From these experimental and computational results, we have shown that EH and EL 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 EH and EL to direct synthetic and engineering efforts.