简介::Twonovelpoly[(3-alkyhhiophene-2,5-diyl)-(benzylidenequinomethane-2,5-diyl)s]derivatives,poly[(3-butylthiophene-2,5-diyl)-(p-N,N-dimethylamino)benzylidenequinomethane-2,5-diyl)](PBTDMABQ)andpoly[-(3-octylthiophene2,5-diyl)-(p-N,N-dimethylamino)benzylidenequinomethane-2,5-diyl)](POTDMABQ),weresynthesized.Thebandgapsofthetwopolymersarecalculatedas1.75eVforPBTDMABQand1.69eVforPOTDMABQ,respectively.Thehomogenousfilmsofthetwopolymerswerepreparedandtheirthird-ordernonlinearopticalpropertieswerestudiedbythebackwarddegeneratefour-wavemixingat532nm.Byusingtherelativemeasurementtechnique,thethird-ordernonlinearopticalsusceptibilitiesofPBTDMABQandPOTDMABQarecalculatedas5.62×10^-9and1.22×10^-8ESU,respectively.Itisfoundthatsubstitutedalkygroupshavestrongeffectsonthebandgapandnonlinearopticalpropertiesofthetwopolymers.Therelativelybigthird-ordernonlinearopticalsusceptibilitiesandsmallbandgapofPOTDMABQresultedmainlyfromthelongeralkylwithstrongelectron-donatingabilitycanenhancethedelocationdegreeofconjugatedπelectronics.