Novel Chalcone Derivatives And Complexes Based On Terpyridyl Ligand:the Syntheses,Structures And Optical Properties

In recent years,much interest has been foucs on the nonlinear optical(NLO)materials for the physicists and chemists.With the development of molecular nonlinear optics,the materials with adjustable NLO properties provides the possibility being used for the information storage,photoelectric modulator,all-optical communication,optical signal processing,optical computing and other fields.The third-order nonlinear optical property can enhance for electron donor and acceptor-substituted chalcone derivatives due to the asymmetry of the backbone.By using the appropriate design strategies,the nonlinear optical coefficient can be enhanced,using as a potential application material.Due to the unique structure,Anthracene and pyrene is considered to be promising nonlinear organic intermediates.The derivative bipyridine ligands are used for the synthesis of complexes and nonlinear area owning to the conjugation of the ? electrons,the photosensitivity and excellent processability.In this paper,we used anthracene and pyrene compounds as the organism to synthesize a series of chalcone compounds.Some complexes were synthesized by solvothermal method using bipyridine and carboxylic acid ligands,and the structures were determined by single crystal X-ray diffraction.The chalcone derivatives were characterized by NMR,IR,elemental analysis and other methods.The research mainly includes the following two sections:1.Chalcone derivatives 1-3 were synthesized by the condensation reaction of 9-anthracen formaldehyde with para-nitro,fluoro substituted and unsubstituted acetophenone,4-6 were synthesized by the 3-(9-anthracene)acrolein with the same acetophenone by the condensation reaction,compounds 7,9 and 10 were also synthesized with 1-pyrene formaldehyde and the same acetophenone,ortho,meta and para-substituted carboxy acetophenone synthesis the compounds 11,12 and 8.Subsequently,the nonlinear optical properties of the compounds were tested by ps and fs Z-scan method,the nonlinear optical properties were researched.1.1 For the compounds from 1 to 3,4 to 6 and 7 to 10,the nonlinear properties of the compounds decrease with the of the electron withdrawing ability of the compound substituents,the nonlinear properties of the compounds containing nitro groups are the strongest in the same series.1.2 In the comparison of compounds 1 and 4,2 and 5,3 and 6,it was found that compounds 2,4,6 containing longer electron channels having higher nonlinear properties than those of compounds 1,3 and 5,whereas the comparison between compounds 4 and compound 1 was most obvious for about three times,indicating that the strong electron-withdrawing group have a great effect on the nonlinear properties of the compound.1.3 Under the femtosecond Z-scan experiments,we comparison the compounds 1 and 7,2 and 9,3 and 10,we found that the compounds containing more aromatic groups had a greater nonlinear performance,especially for compound 7,the nonlinear performance has about ten times increae than compound 1.1.4 By studying the nonlinear properties of the chalcone compounds 8,11 and 12 in different positions,we found that the nonlinearity of the meta-substituted chalcone compound 12 was the best,compound 8 is weakest.It has been found that the para-substituted chalcone compounds have the best nonlinear performance.The possible explanation is the difference for substituents,the carboxyl group acts as an electron withdrawing group.The molecular structure of the compound can be similar treat as the D-A-A type,electrons are transferred to the donor end from the receptor end.Due to the different position and the spatial configuration,thus result in the difference nonlinear performance.Through the research about the nonlinear properties of the chalcone compounds,we found that compound 7 exhibited the strongest nonlinear properties,which could be used as the nonlinear optical material.Strong electron-withdrawing groups,long electron channels,and large aromatic rings have greatly contributed to improve the nonlinear properties of the chalcone compounds.2.Eight complexes were obtained by solvothermal method using bipyridine ligand and carboxylic acid ligands with the metal Mn(?),Co(?)and Ni(?),which are [Mn(Py-terpy)Cl2]}n(13),{[Mn(Py-terpy)(BDC)(H2O)3]}n(14),{[Mn(Py-terpy)(H2O)3(HBTC)]}n(15),{[Mn(Py-terpy)(H2O)(BTEC)0.5]}n(16),{[Co2(Py-terpy)(H2O)3(BDC)1.5Cl]}n(17),{[Co(Py-terpy)(H2O)3(HBTC)]}n(18),{[Co2(Py-terpy)(H2O)5(BTEC)]}n(19),{[Ni2(Py-terpy)(H2O)3(BDC)1.5Cl]}n(20).The structure of the complexes was analysised by X-ray diffraction,the basic properties of the complexes were researched,the solvent stability of the complexes,also with the research about the nonlinear optics of the complexes.