| The ladder-type conjugated polymer has a large ?-conjugated system,and because of its unique structure,it has special physicochemical properties and self-assembly properties,it also has a wide application in the fields of organic field effect transistors,organic light emitting diodes,and solar cells.The synthesis of ladder-type conjugated polymers usually need to go through two or more steps,so it may lead to defects in the structure of the polymer,which may affect the photovoltaic properties of this kind of material.Therefore,it is important to develop a one-step route synthesis of ladder-type conjugated polymers.In this thesis,the ladder-type conjugated polymers containing carbazole units were synthesized by one-step method.The main contents of the thesis are as follows:1.Ladder-type conjugated polymer containing amide bridge is synthesized by one-step method.Compound 4 is synthesized by nitration reaction using 2,7-dibromocarbazole as raw material.Compound 4 and tin chloride generate compound 5 through reduction reaction.Compound 6 is synthesized by Miyaura boric acid esterification reaction of diethyl2,5-dibromoterephthalate and bis(pinacolato)diboron.Compound C1 can be synthesized through Suzuki coupling and ammonolysis reaction of compound 5 and2-(ethoxycarbonyl)benzeneboronic acid pinacol ester.Polymer P1 is obstained by one-step method through Suzuki coupling and ammonolysis reaction using compound 5 and compound6 as monomers.The maximum UV-vis absorption peaks of C1 and P1 in tetrahydrofuran(THF)solution are 383 nm and 435 nm,respectively;the fluorescence emission peaks of C1 and P1 in THF solution are located at 471 nm,499 nm and 526 nm.The temperature of weight loss rate 5% of C1 and P1 are 364 C and 370 C,indicating that C1 and P1 have excellent thermal stability.The highest occupied molecular orbital(HOMO),lowest unoccupied molecular orbital(LUMO),and band gap of P1 are-5.62 eV,-3.21 eV,and 2.41 eV,respectively.2.Ladder-type conjugated polymer containing carbon-nitrogen bridge is synthesized by one-step method.Compound 7 is reacted with bis(pinacolato)diboron through Miyaura boric acid esterification reaction to synthesize compound 8,further compound C2 is synthesized by Suzuki coupling and addition reaction of compound 8 and 2-bromoaniline.Polymer P2 is obstained by one-step method through Suzuki coupling and addition reaction using compound5 and compound 8 as monomers.The maximum UV-vis characteristic absorption peaks of C2 and P2 in THF solution are 306 nm and 433 nm,respectively;the fluorescence emission peaks of C2 and P2 in THF solution are located at 419 nm,440 nm and 511 nm,respectively.The temperature of weight loss rate 5% of C2 and P2 are 360 C and 387 C,indicating that C2 and P2 have excellent thermal stability.The HOMO,LUMO,and band gap of P2 are-5.10 eV,-2.65 eV,and 2.41 eV,respectively.3.Ladder-type conjugated polymer containing ester bridge is synthesized.Compound 9 is synthesized using o-dianisidine as raw material,compound 9 synthesized compound 10 through nitration reaction.Compound 11 containing carbazole unit is obtained after ring-closing reaction of compound 10,compound 11 generate compound 12 through Hofmann alkylation reaction.Compound 13 is synthesized through Miyaura boric acid esterification reaction with compound 12 and bis(neopentyl glycolato)diboron.Polymer P3 is synthesised by Suzuki coupling reaction using compound 6 and compound 12 as monomers and generate P4 through ester exchange reaction.Polymer P5 is obtained by Suzuki coupling reaction using compound 13 and diethyl2,5-dibromothieno[3,2-b]thiophene-3,6-dicarboxylate as monomers and generate P6 through ester exchange reaction.The maximum UV-vis absorption peaks of P3 and P4 in THF solution are 365 nm and 474 nm,respectively.The fluorescence emission peaks of P3 and P4 in THF solution are 551 nm and 554 nm,respectively.The temperature of weight loss rate 5%of P3,P4,P5 and P6 are 367 C,387 C,323 C and 383 C,indicating that P3,P4,P5 and P6 have excellent thermal stability. |
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