| In recent years,the design and synthesis of organic functional materials have attracted wide attention.Among them,nonogrids that our group hasstudied is obviously different from the previous organic macrocyclic compounds.Currently,the monogrids that have been explored mainly include ladder-type,windmill-type,diamond-type,tic-tac-toe-type,and angle-lost-type.Unlike traditional organic macrocyclic,nonogrids have regular structures,measurable lengths and well-defined vertices.Their excellent physicochemical stability and luminescence stability,which make them widely used in the field of organic electronic devices.However,there are still deficiencies in the structure and synthesis of nonogrids: 1.Many isomers leading to separate difficultly;2.Complicated synthesis steps and long synthesis time.In order to solve such problems,we further designed a series of novel nanogrids based on the existing tic-tac-toe-type nonogrids: 1.Introducing spiro[fluorine-9,9-xanthene] derivatives to enhance their optoelectronic properties;2.Introducing spiro fluorene to increase the structural rigidity,and reduce the number of isomers;3.One-step synthesis of wellshaped nanogrids with strong rigidity,few isomers and regular structure based on Yamamoto coupling reaction.The main research contents are as follows:(1)The conditions were optimized for the synthesis of spiro and spiro structures.According to the characteristics of Friedel-Crafts(F-C)reaction,the controlled variable method was used to explore the effects of acid equivalence ratio,reaction temperature,reaction concentration,reaction time,and reactant equivalence ratio on the reaction acids.The experimental results showed that when,the ratio of catalyst(methanesulfonic acid)was 10 times,the reaction concentration was 0.1m M,the solvent was o-dichlorobenzene,the maximum yield of xantherospiro was 50% when the reaction is carried out at 160 °C for 24 h.Then,a new well-shaped nangrids GSFX based on xantherspiro with strong rigidity and few isomers was synthesized via Yamamoto coupling reaction,and its structure was confirmed by NMR and MALDITOF-MS.(2)On the basis of the synthesis in the previous chapter,further work was carried out on the nanogrids GSFX.First,the absorption and emission spectra of GSFX in solution and film were tested respectively,and it was found that the emission spectrum of GSFX in film had a red-shift phenomenon.Therefore,the molecule GSFX was compared with the tic-tac-toe-type nanogrids GSBF with the sane phenomenon.The experimental results showed that this phenomenon of red shift of emission spectrum was caused by the intermolecular π-π stacking,and the rigidity and regularity of the molecules are the necessary conditions to trigger this special luminescence.From the perspective of molecular structures,GSFX has stronger regularity and molecular rigidity than GSBF.(3)In this chapter,indenofluorenone wasintroduced to replace fluorenone to explore the optimal reaction conditions when using indenofluorenone and resorcinol as raw materials.The results showed that the optimal reaction conditions were: indenofluorenone(0.564 g,2 mmol),resorcinol(1.88 g,20mmol)and p-toluenesulfonic acid(4.5 g,10 mmol),o-dichlorobenzene(60 m L),and the reaction was carried out at 160 °C for 72 h,the spiro product was obtained in 38.14% yield.Its structure was determined by NMR and MALDI-TOF-MS.On the basis,we designed a new kind of tic-tac-toe-type nanogrids based on indenofluorenone with stronger rigidity and more regular structures compared with GSFX,which was synthesized by one-step F-C reaction using indenofluorenone and resorcinol as substrates,and the preliminary separation and MALDI-TOF-MS characterization confirmed that this reaction route was feasible.In this paper,different spiro rings were used as substrates to synthesize novel tic-tac-toe-type nanogrds with strong structural rigidity and few isomers based on Yamamoto coupling reaction,which enriched the types of nanogrids and provided new ideas for the design of new nonogrids in the future. |
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