Study On The Synthesis Of Anthracene Derivatives And Configuration, Properties Of Novel Anthracene Conjugate Molecules

With the large π-conjugated structure, acene derivatives have good applicationprospects in organic photoelectric material. It is an effective method to achieve anaromatic ring expansion mediated by zirconium coupling to prepare acene derivatives.The synthesis route of tetrahydrogenated anthracene derivatives were studied inthis paper. With a series of experiments, we made the direct coupling reaction ofsubstituted with trimethylsilyl group of zirconacyclopentadienes on2,5positions with1,2,4,5-Tetraiodobenzene and obtained tetrahydrogenated anthracene and itsderivatives. We expanded the methodology range of the coupling ofzirconacyclopentadienes and halogenated aromatic.Two kinds of novel anthracene derivatives were designed, including differentconjugated group (2-thienyl acetylene, phenylacetylene,2-pyridylacetylene)-substituted anthracene derivatives on2,3positions (six molecules) andsilicon-substituted anthracene dialkyne (nine molecules).Quantum chemistry calculation had significant application in the research of theproperties of photoelectric materials, especially for micro understanding andprediction of the chemical bond, optical and electronic structure of conjugated system,which agreed well with the experimental results. Gaussian03quantum chemistrysoftware, density functional theory and B3LYP method at6-31G(d) level were used toget the optimized geometries of substituted with conjugated group of anthracenederivatives on2,3positions and silicon-substituted anthracene dialkyne, and then westudied their ground state geometry, bandgap, frontier molecular orbitals, ionizationenergy, electron affinity, reorganization energy. Time-dependent density functiontheory and B3LYP method at6-31G(d) level were used to study their absorptionspectra.The results indicate that both the two kinds of molecules have a highHOMO-LUMO energy gap (around3eV), they have a good oxidation-reductionstability. In the conjugated group substituted anthracene derivatives on2,3positions,2,3-bis(thienyl-2-ylethynyl)-9,10-bis(trimethylsilyl)anthracene which is named asmolecule1, it has the lowest hole recombination enery (0.165eV) so that it is expected to be used as hole transport material. In the silicon-substituted anthracene dialkyne,(2-(dimethyl(thienyl-2-ylethynyl)silyl)-3-(thiophen-2-ylethynyl)-9,10-bis-(trimethylsi-lyl)anthracene, which is named as molecule7, its hole reorganization energy λ(h) andelectron reorganization energy λ(e) is quite close, the λ(e) is just higher by0.058eVthan λ(h), so it has a good balance of hole and electron transport, it is expected to beused as ambipolar transport material. The method proposed in this paper providedideas and guidance for the development of organic electroluminescent materials.