| This project is cooperated between P.AUDEBERT's group which belongs to lab of CNRS-PPSM and our group.Based on the previous work,this thesis was forcused on preparing some hindered or electron-withdrawing substituents s-tetrazine and studing their electrochemical and spectroscopic properties.Nineteen new s-tetrazines,with big steric substituted group,have been synthesized for the first time using 3,6-dichlorotetrazine as the starting material,and which condensed with adamantanol,broneol,cholesterol,9-fluorenylmethanol etc. Among them there are nine derivatives with big steric hindrance and electron withdrawing group.The fluorescence properties of several new s-tetrazines were initially investigated,and the result showed that(1) all of the compounds have two spectral bands.The strong band at 300～350nm can be attributed to aπ-π~* allowed transition while the one at 500～550nm corresponds to an n-π~* transition.The UV absorb band is affected by the substituted group,(2) the fluorescence emission bands of these compounds are about 540nm～580nm,(3) quantum yield is also affected by the substituted groups.The compounds 27,29,38 which are with bulky alkoxy substituents have higher quantum yield.Especially,38,quantum yield is 0.62 which is the highest one among the s-tetrazines,(4) the s-tetrazines bearing two alkoxy substituents,display fluorescence but lower than the one alkoxy substituents.The investigation of the electrochemical behavior of some tetrazines indicated that(1) all compounds display reversible CV's,with potentials depending on the electron affinity of the substituent,(2) according to the calculations of the different energys with different structures and kinetic parameters,we know that the molecule geometry have no influence on the electron transfer rate,(3) another point is the alkoxy substituents tetazine can be electrochemically reduced through a two electrons process, but chemical reversibility.It makes them potentially interesting compounds for energy storage. |
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