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

被引：56

作者：

Vladimirova, Kseniya G. ^{[1
,2
]}

Freidzon, Alexandra Ya. ^{[1
]}

Kotova, Oxana V. ^{[2
]}

Vaschenko, Andrei A. ^{[3
]}

Lepnev, Leonid S. ^{[3
]}

Bagatur'yants, Alexander A. ^{[1
]}

Vitukhnovskiy, Alexel G. ^{[3
]}

Stepanov, Nickolai F. ^{[2
]}

Alfimov, Michael V. ^{[1
]}

机构：

[1] Russian Acad Sci, Photochem Ctr, Moscow 117421, Russia

[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia

[3] Russian Acad Sci, PN Lebedev Phys Inst, Moscow 119991, Russia

来源：

INORGANIC CHEMISTRY | 2009年 / 48卷 / 23期

基金：

俄罗斯基础研究基金会;

关键词：

DENSITY-FUNCTIONAL THEORY; AB-INITIO; EXCITED-STATES; EXCITATION-ENERGIES; CRYSTAL-STRUCTURE; SALEN; APPROXIMATION; MECHANISM; ZN(II); NI(II);

D O I：

10.1021/ic9015004

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Tetradentate Schiff bases (H2L1), derivatives of salicylic aldehyde (H2L, 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, I R 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 TID DFT/PBEO calculations reveals the crucial importance of the inclusion of the exact exchange in the Exc functional for the further correct description of potential energy surfaces of excited states for the systems studied.

引用

页码：11123 / 11130

页数：8

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