title: Theoretical study of structure and electronic absorption spectra of some Schiff bases and their zinc complexes.
abstract: Tetradentate Schiff bases (H(2)L(i)), derivatives of salicylic aldehyde (H(2)L(1), H(2)L(2)) or o-vanillin (H(2)L(3), H(2)L(4)) 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.
authors.affiliation: Photochemistry Center, Russian Academy of Sciences, ul. Novatorov 7a, 117421 Moscow, Russia. kgvladi@gmail.com
authors.forename: Kseniya G
authors.initials: KG
authors.lastname: Vladimirova
authors.forename: Alexandra Ya
authors.initials: AY
authors.lastname: Freidzon
authors.forename: Oxana V
authors.initials: OV
authors.lastname: Kotova
authors.forename: Andrei A
authors.initials: AA
authors.lastname: Vaschenko
authors.forename: Leonid S
authors.initials: LS
authors.lastname: Lepnev
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Bagatur'yants
authors.forename: Alexei G
authors.initials: AG
authors.lastname: Vitukhnovskiy
authors.forename: Nickolai F
authors.initials: NF
authors.lastname: Stepanov
authors.forename: Michael V
authors.initials: MV
authors.lastname: Alfimov
mesh_terms: D018360:Crystallography, X-Ray; D004583:Electrons; D008024:Ligands; D008956:Models, Chemical; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D012545:Schiff Bases / Q000737:chemistry*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics; D015032:Zinc / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D012545:Schiff Bases; D015032:Zinc