| Conjugated polymers as semiconducting materials have attracted broad academic and industrial interest for various optoelectronic devices. In particular, their applications in polymer light-emitting diodes(PLEDs), polymer solar cells(PSCs), and organic field-effect transistors(OFETs) offer opportunities for the resolution of energy issues as well as the development of display and information technologies. In comparison with inorganic materials and small-molecule organic semiconductors, conjugated polymers provide several advantages including low cost, light weight, and good flexibility. More importantly, soluble polymer semiconducting materials can be readily processed and easily printed, removing the conventional photolithography for patterning, which is a critical issue for the realization of large-scale roll-to-roll processing of printed electronics.In the recent years, the s-triazine derivatives have drawn much interest due to their high-electron affinity and structural symmetry. Extensive work on s-triazine derivatives and polymer-containing triazine unit with different aromatic rings has been done for their ability to be as electron injection and transport, luminescent, nonlinear-optical, and two-photon absorption materials as well as the building block for metal-containing supramolecular architectures, and so forth. In this dissertation, we designed and synthesized series of conjugated polymers based on s-triazine unit, and structures of the polymers were characterized by infrared spectroscopy(FT-IR) and nuclear magnetic resonance spectroscopy(1H-NMR). In the meantime, Optical, electrochemical, acidochromic and crystalline properties of polymers were studied extensively. The detailed studies and results are summarized as follows:1. Three kinds of polymers of poly(p-phenylene-ethynylenes)(P1 and P2) and polyfluorenes(P3) containing 2-diisopropylamino-s-triazine unit were synthesized using 2-diisopropylamino-4,6-dichloro-s-triazine as comonomer via metal-catalyst reactions. The UV-Vis maximum absorption peaks of P1 and P2 appear at 440 nm,416 nm in solution and at 441 nm, 419 nm in film state, respectively. The PL emission peaks of P1 and P2 appear at 478 nm, 474 nm in solution and at 531 nm, 527 nm in film state, respectively. P1 and P2 emit green light, and the quantum efficiencies are 67.7% and 42.1%, respectively. The maximum absorption peaks of P3 appear at 368 nm in solution and at 370 nm in film state, respectively. The PL emission peaks of P3 appear at 410 nm in solution and at 411 nm in film state, respectively. P3 emit blue light, and the quantum efficiency is 24.9%. In comparison with P3, P1 and P2 have a better crystallinity. From cyclic voltammetry measurement, it was found that these reported polymers only present certain p-doping behavior. After studying acidochromisim of polymers in chloroform-trifluoroacetic acid solution, it was found that P3 has better acidochromic behavior than P1 and P2, and P3 exhibit linear relationship in certain acid concentration region.2. Five kinds of polymers of polythiophenes(P4, P5, P6, P7, P8) containing 2-diisopropylamino-s-triazine were synthesized using 2-diisopropylamino-4,6-dichloros-triazine as comonomer via metal-catalyst reactions. The UV-Vis maximum absorption peaks of P4, P5, P6, P7 and P8 appear at 354 nm, 395 nm, 371 nm, 371 nm, 371 nm in solution and at 357 nm, 365 nm, 384 nm, 373 nm, 373 nm in film state, respectively. The PL emission peaks of P4, P5, P6, P7 and P8 appear at 454 nm, 442 nm, 478 nm, 549 nm, 527 nm in solution and at 514 nm, 493 nm, 575 nm, 561 nm, 575 nm in film state, respectively. These derived P4, P5, P6, P7 and P8 emit green light, and the quantum efficiencies are 10.7%, 8.3%, 7.5%, 7.8% and 5.6%, respectively. In comparison with P5, P4 has certain crystallinity. P6, P7 and P8 containing 3-alkylthiophene ring in polymer main chain show lower crystallinity. From cyclic voltammetry measurement, it was found that these reported polymers only present certain n-doping behavior. After studying acidochromisim of polymers in chloroform-trifluoroacetic acid solution, comparing to P5 containing3,4-ethylenedoxy thiophene moiety, it was found that P4, P6, P7 and P8 containing thiophene or 3-alkyl thiophene ring in polymer main chain have better acidochromic behavior and display linear relationship in certain acid concentration region..3. Two kinds of homopolymers(P9 and P10) of 2-diisopropylamino-4,6-bis(thien-2-yl)-s-triazine and 2-diisopropylamino-4,6-bis[(3,4-ethylenedioxythienyl)-striazine were prepared using ferric trichloride as a oxidant via oxidative polymerization. The UV-Vis maximum absorption peaks of P9 and P10 appear at 303 nm, 461 nm in solution and at 309 nm, 489 nm in film state. The PL emission peaks of polymers appear at 507 nm and 511 nm. Comparing to P9, P10 shows better crystallinity. From cyclic voltammetry measurement, it was found that P10 shows excellent n-doping behavior except from P9 which has no electrochemical activity. After studying acidochromisim of polymers in chloroform-trifluoroacetic acid solution, it was found that P10 has a great acidochromic behavior than P9.4. Four kinds of polymers of poly(p-phenylene-ethynylenes)(P11 and P12), polyfluorenes(P13) and polythiophenes(P14) containing 2-diisopropylamino-4,6-bis(thien-2-yl)-s-triazine unit were synthesized using 2-diisopropylamino-4,6-bis[5′-bromo-(thien-2-yl)]-s-triazine as comonomer via metal-catalyst reactions. The UV-Vis maximum absorption peaks of P11, P12 and P14 appear at 430 nm, 430 nm, 430 nm in solution and at 448 nm, 445 nm, 430 nm in film state, respectively. The PL emission peaks of P11, P12 and P14 appear at 480 nm, 483 nm, 518 nm in solution and at 538 nm, 539 nm, 548 nm in film state, respectively. P11, P12 and P14 emit green light, and the quantum efficiencies are 80.0%, 66.8% and 28.0%, respectively. The maximum absorption peaks of P13 appeared at 405 nm in solution and at 408 nm in film state, respectively. The PL emission peaks of P13 appear at 452 nm in solution and at 482 nm in film state, respectively. P3 emits blue light, and the quantum efficiency is 96.5%. In comparison with P13 and P14, P11 and P12 have better crystallinity. From cyclic voltammetry measurement, it was found that these reported polymers only present excellent n-doping behavior. After studying acidochromisim of polymers in chloroform-trifluoroacetic acid solution, it was found that all polymers show better acidochromic behavior, and P13 and P14 have great acidochromic sensitivities than P11 and P12, and exhibit linear relationship in certain acid concentration region.5. Three kinds of polymers of poly(p-phenylene-ethynylenes)(P15 and P16) and polyfluorenes(P17) containing 2-diisopropylamino-4,6-bis(3,4-ethylenedioxythienyl)-s-triazine unit were synthesized using 2-diisopropylamino-4,6-bis[5′-bromo-(3,4-ethylenedioxythienyl)]-s-triazine as comonomer via metal-catalyst reactions. The UV-Vis maximum absorption peaks of P15, P16 and P17 appear at 443 nm, 443 nm, 4431 nm in solution and at 472 nm, 456 nm, 410 nm in film state, respectively. The PL emission peaks of P15, P16 and P17 appear at 507 nm, 511 nm, 543 nm in solution and at 540 nm, 545 nm, 556 nm in film state, respectively. P15, P16 and P17 emit green light, and the quantum efficiencies are 85.7%, 85.2% and 64.4%, respectively. In comparison with P17, P15 and P16 have a better crystallinity. From cyclic voltammetry measurement, it was found that these reported polymers only present certain n-doping behavior. After studying acidochromisim of polymers in chloroform-trifluoroacetic acid solution, it was found that all polymers show better acidochromic behavior, and P17 has great acidochromic sensitivity than P15 and P16.6. Two kinds of polymers of poly(p-phenylene-ethynylenes)(P18, P19) containing 2-diisopropylamino-4,6-bis[2′-(3,4-ethylenedoxythienyl)methylene]hydra-zinyl]-1,3,5-triazine unit were synthesized using 2-diisopropylamino-4,6-bis[2′-(5′-bromo-3,4-ethylenedoxythienyl)methylene)hydrazinyl]-1,3,5-triazine as comonomer via metal-catalyst reactions. The UV-Vis maximum absorption peaks of P18 and P19 appear at 452 nm, 457 nm in solution and at 452 nm, 457 nm in film state. The PL emission peaks of polymers appear at 468 nm and 474 nm. These polymers emit green light, and the PL emission peaks of polymers appear at 543 nm and 549 nm. Both of polymers have certain crystallinity. From cyclic voltammetry measurement, it was found that these reported polymers only present certain p-doping behavior. One kind of homopolymer of 2,4,6-tris[(2′-(3,4-ethylenedioxythienyl)methylene)-hydrazinyl]-1,3,5-triazine were prepared using ferric trichloride as a oxidant via oxidative polymerization. The maximum absorption peaks of polymer P20 appear at 484 nm in solution and at 500 nm in film state, respectively. The polymer emits red light, and the PL emission peak of polymer appears at 522 nm in solution. From cyclic voltammetry mesurement, it was found that polymer P20 only presents excellent n-doping behavior. After studying acidochromisim of P18, P19 and monomer 2,4,6-tris[(2′-(3,4-ethylenedioxythienyl)methylene)-hydrazinyl]-1,3,5-triazine, it was found that all of them show better acidochromic behavior and exhibit linear relationship in certain acid concentration region. |
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