Molecular Design,synthesis And Properties Of CPDT-based Ladder-type Gridarene

4H-Cyclopenta[2,1-b:3,4-b’]dithiophene(CPDT),as a kind of molecular framework with rigid plane fluorene-like structure,its photoelectric material has low band gap,high The advantages of excellent electrical conductivity and strong intermolecular interaction have been widely used in the field of plastic electronics.CPDT can be used as a molecular module to be functionalized at its bridging carbon,and various substituents(such as redox active moieties,alkyl chains,etc.)can be introduced.These excellent monomer properties and controllable functionalization make its application in optoelectronic materials more prominent.At present,the development of4H-cyclopenta[2,1-b:3,4-b’]dithiophene and its derivatives is very rapid,and there are many research reports on it.It is one of the most widely used electron donor structures.It has very important applications in organic solar cells(OSCs),organic field effect transistors(OFETs),organic light-emitting diodes,organic thermoelectrics,Li-ion batteries,organic flash memory and other fields.Our research group is committed to the research of nanogridarenes.Among them,the research on the fluorenyl ladder-type gridarene is the most extensive and in-depth.The mature experimental conditions of the ladder-type gridarene and the perfect Friedel-Crafts reaction system enable us to have a deep understanding of the construction of the ladder-type gridarene.Therefore,we combined the fluorene-like structure 4H-cyclopentan[2,1-b:3,4-b’]dithiophene and the related theory and practice of the ladder-type gridarene to carry out a systematic study.The related work will mainly focus on the following three Expand the aspects:First,on the basis of the research on the CPDT reaction sites in the early stage of the group,in this chapter we designed and synthesized CPDT-based di-tertiary alcohols and studied their performance.Firstly,the Suzuki coupling reaction was carried out with CPDT mono-tertiary alcohol as a substrate to obtain dimerized CPDT tertiary alcohol with a yield of 9%.The dimer tertiary alcohol DPhCDTOH theoretically has a pair of enantiomers(rac)and a meso(meso).In this reaction,two isomers were observed by performing TLC climbing on DPhCDTOH.The two isomers were separated by column chromatography to obtain meso-DPhCDTOH and rac-DPhCDTOH with yields of 5%and 4%,respectively.Finally,the two isomers were characterized by film-ray diffraction,powder-ray diffraction and AFM tests,and it was found that there was no obvious difference between them.However,in field effect transistors memory,meso-DPhCDTOH thin film devices have certain performance,with a mobility of 0.0095 cm~2/Vs and a window of 17.37 V,while rac-DPhCDTOH thin film devices have almost no storage performance.Second,we used the I-shape synthesizer DPhCDTOH and dithiophene as raw materials,and the ladder-type gridarene was not obtained under Friedel-Crafts reaction conditions.This may be due to the distortion of the conformation caused by the force of the S-S atom in DPhCDTOH and the corresponding trapezoid could not be obtained.grid.In order to verify this phenomenon and increase the yield of dimerized tertiary alcohols,we used S┄O supramolecular force to insert1,4-dimethoxyphenyl groups in the middle of DPhCDTOH molecules to synthesize a new type of CPDT-based The yield of the di-tertiary alcohol DPhMeOCPDTOH reached 82%.Subsequently,the Friedel-Crafts reaction between DPhMeOCPDTOH and dithiophene resulted in a ladder-type gridarene(G-DPhMeOCPDT)with only a trace yield,and a U-shaped structure(U-DPhMeOCPDT)with a yield of 10%.In order to obtain a trapezoidal lattice with a high yield,we used a U-shaped structure to react with DPhMeOCPDTOH,and as a result,a trapezoidal lattice was obtained with a yield of 5%.The structure of U-shaped and trapezoidal lattices is confirmed by MALDI-TOF,hydrogen spectrum and carbon spectrum.Third,On the basis of the second part,we carried out a series of characterization tests on DPhMeOCPDTOH,U-shaped structure and trapezoidal lattice.It is found that there is no obvious difference in the absorption-emission spectra,and the overall crystallinity is very poor.AFM test shows that the film-forming properties of U-DPhMeOCPDT are better than those of DPhMeOCPDTOH and G-DPhMeOCPDT.In the electrochemical actuator,it is found that DPhMeOCPDTOH,U-DPhMeOCPDT and G-DPhMeOCPDT have certain performance in the electrochemical actuator.Among them,G-DPhMeOCPDT has the best performance,with a bending strain of 0.2941%;in the capacitance test,it is found that Ph Me OCDTOH,U-DPhMeOCPDT and G-DPhMeOCPDT have certain performance in capacitors.Among them,the specific capacitance of G-DPhMeOCPDT is the highest,reaching 0.1371μF/mm~2,indicating that gridding is conducive to the enhancement of charge storage performance,and the ring closure is also conducive to electrochemical execution The insertion and extraction of ions in the device provide a new research direction for the application of gridarenes.