| Perylene diimides(PDIs),naphthalene diimides(NDIs)and their derivatives are excellent semiconductors.PDIs and NDIs polymers have the advantages of solution processing and good film-forming ability,while they have limited applications because of low carrier mobility.This study focuses on high mobility polymeric electron acceptors based on PDIs and NDIs.It includes the following two parts.(1)Design,synthesis,and application of high molecular weight and high electron mobility conjugated polymers of semi-perfluoroalkylated perylene diimides.The five polymers were synthesized by Stille coupling reaction of semi-perfluoroalkyl modified brominated PDIs(Br-CFCH-PDI)and donor unit(thiophene,bithiophene and terthiophene).It was found that these polymers had a strong absorption at 300-800 nm,low LUMO energy level(-4.01?-4.21 e V),high thermal stability(Td>370 oC),strong hydrophobicity(CA>108 o),high molecular weight(the maximum Mn reaches 94.8k Da)and high electron mobility(the largest 8.40 x 10-3 cm2?V–1?s–1).Obviously,these polymers have excellent electron transport capabilities.(2)Design,synthesis and properties of solution processable ladder-type conjugated polymers without alkyl chains.To process ladder polymers with organic acids with low-boiling points(such as CF3COOH),Lewis base centers(Br,N)were introduced.To adjust their absorption and energy levels,different conjugated cores were adopted.Monomers(M1-M4)were synthesized through a multi-step reaction pathway(esterification,coupling,addition,substitution,and hydrolysis)with 1,4,5,8-naphthalenetetracarboxylic acid dianhydride as the starting material.Polymers LP1-LP4 were obtained by the polycondensation of monomers with 1,2,4,5-Benzenetetraamine in polyphosphoric acid at high temperature.The results showed that polymers solubility in concentrated H2SO4 was much better than that of BBL,and the solubility of LP4 reached 5 mg/m L in CF3COOH,which was favorable for solution processing. |
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