Theoretical Study of Structure and Electronic Absorption Spectra of Some Schiff Bases and Their Zinc Complexes

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• 作者：Kseniya G. Vladimirova ; Alexandra Ya. Freidzon ; Oxana V. Kotova ; Andrei A. Vaschenko ; Leonid S. Lepnev ; Alexander A. Bagatur’ ; yants ; Alexei G. Vitukhnovskiy ; Nickolai F. Stepanov ; Michael V. Alfim
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：December 7, 2009
• 年：2009
• 卷：48
• 期：23
• 页码：11123-11130
• 全文大小：903K
• 年卷期：v.48,no.23(December 7, 2009)
• ISSN：1520-510X

文摘

Tetradentate Schiff bases (H₂Lⁱ), derivatives of salicylic aldehyde (H₂L¹, H₂L²) or o-vanillin (H₂L³, H₂L⁴) with ethylenediamine or o-phenylenediamine as a bridge, and their zinc complexes were studied experimentally and theoretically in view of their possible application as emitters in organic light emitting diodes (OLEDs). The composition of thin films of the complexes was analyzed using a combination of different experimental and molecular modeling techniques taking into account changes in the Gibbs free energy of dehydration and dimerization reactions. The absorption spectra of the initial Schiff bases were investigated in methanol solutions, while the absorption spectra of their zinc complexes were investigated in thin films. Experimental results of elemental analysis, IR spectroscopy, laser desorption/ionization mass spectrometry (LDI MS), and X-ray diffraction as well as theoretical analysis of electronic absorption spectra by the quantum-chemical TD DFT method demonstrate that thin films of the zinc complexes contain binuclear anhydrous molecules. This conclusion should be taken into account when considering both transport and luminescence properties of these complexes in OLED heterostructures. A comparison of the results of CIS, TD DFT/PBE, and TD DFT/PBE0 calculations reveals the crucial importance of the inclusion of the exact exchange in the E_XC functional for the further correct description of potential energy surfaces of excited states for the systems studied.