In this study,a family of three benzodifurandione-baseddonor–acceptor(D–A)copolymers,namelypoly[3,7-bis((E)-1-(4-octadecyldocosyl)-2-oxo-6-yl-indolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dionealt-(E...In this study,a family of three benzodifurandione-baseddonor–acceptor(D–A)copolymers,namelypoly[3,7-bis((E)-1-(4-octadecyldocosyl)-2-oxo-6-yl-indolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dionealt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PBDO-DTE),poly[3,7-bis((E)-7-fluoro-1-(4-octadecyldocosyl)-2-oxo-6-yl-indolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione-alt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PFBDO-DTE),and poly[(3E,7E)-3,7-bis(1-(4-octadecyldocosyl)-2-oxo-6-yl-1,2-dihydro-3Hpyrrolo[2,3-b]pyridin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione-alt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PNBDO-DTE),was designed and synthesized by employing aldol polycondensation reactions between benzodifurandione and bisindolin-2-ones in high yields.Further incorporation of fluorine or sp2-hybridized nitrogen atoms on the bisindolin-2-one unit induced S…F or S…N nonbonding interactions-locked polymeric conjugated backbones for PFBDO-DTE and PNBDO-DTE,respectively.Ultraviolet photoelectron spectroscopy and inverse photoemission spectroscopy measurements revealed that the two copolymers have lower frontier molecular orbitals than that of PBDO-DTE.Atomic force microscopy and two-dimensional grazing-incidence wide-angle X-ray scattering investigations indicated the PNBDO-DTE copolymer could form more ordered molecular aggregation in the solid state than PBDO-DTE and PFBDO-DTE copolymers.We fabricated thin film transistors based on these copolymers on plastic polyethylene terephthalate substrates,and they all showed ambipolar charge transport characteristics.Among them,the PNBDO-DTE-based devices afforded optimal charge transport characteristics with high hole and electron mobilities of 5.16 and 1.33cm^(2)V^(−1)s^(−1),respectively.Our study highlights that aldol polycondensation would be an extremely useful protocol in constructing high-performance polymer semiconductors.展开更多
基金made possible as a result of a generous grant from the Beijing Municipal Natural Science Foundation(grant no.2212054)the National Natural Science Foundation of China(grants nos.22075294,22275194,22175021,22021002)Beijing National Laboratory for Molecular Sciences(grant no.BNLMSCXXM-202101).
文摘In this study,a family of three benzodifurandione-baseddonor–acceptor(D–A)copolymers,namelypoly[3,7-bis((E)-1-(4-octadecyldocosyl)-2-oxo-6-yl-indolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dionealt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PBDO-DTE),poly[3,7-bis((E)-7-fluoro-1-(4-octadecyldocosyl)-2-oxo-6-yl-indolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione-alt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PFBDO-DTE),and poly[(3E,7E)-3,7-bis(1-(4-octadecyldocosyl)-2-oxo-6-yl-1,2-dihydro-3Hpyrrolo[2,3-b]pyridin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione-alt-(E)-1,2-di(2,2′-bithiophen-5-yl)ethene](PNBDO-DTE),was designed and synthesized by employing aldol polycondensation reactions between benzodifurandione and bisindolin-2-ones in high yields.Further incorporation of fluorine or sp2-hybridized nitrogen atoms on the bisindolin-2-one unit induced S…F or S…N nonbonding interactions-locked polymeric conjugated backbones for PFBDO-DTE and PNBDO-DTE,respectively.Ultraviolet photoelectron spectroscopy and inverse photoemission spectroscopy measurements revealed that the two copolymers have lower frontier molecular orbitals than that of PBDO-DTE.Atomic force microscopy and two-dimensional grazing-incidence wide-angle X-ray scattering investigations indicated the PNBDO-DTE copolymer could form more ordered molecular aggregation in the solid state than PBDO-DTE and PFBDO-DTE copolymers.We fabricated thin film transistors based on these copolymers on plastic polyethylene terephthalate substrates,and they all showed ambipolar charge transport characteristics.Among them,the PNBDO-DTE-based devices afforded optimal charge transport characteristics with high hole and electron mobilities of 5.16 and 1.33cm^(2)V^(−1)s^(−1),respectively.Our study highlights that aldol polycondensation would be an extremely useful protocol in constructing high-performance polymer semiconductors.
