Synthesis And Application Of Diarylethene-based Photoswitchable Polymeric Materials

As a kind of stimulation,light provides a reliable foundation for intelligent design of photoswitchable materials due to its advantages of high spatial and temporal resolution,and digital management.At present,the photochemical properties of the photoswitchable compound diarylethylene have become a hot topic.Based on this,this paper synthesized several diarylethylene derivatives and introduced them into the polymeric system,investigated systematically their optically switchable properties,and explored the potential for information encryption,display lighting,logic gates,cell imaging and controlled photowritable/erasable patterning,etc.The specific research contents are as follows:(1)Based on the mechanism of fluorescence resonance energy transfer(FRET),with blue fluorescent dye 4-ethoxy-9-allyl-1,8-naphthalimide(EANI),green fluorescent dye 2-((7-nitrobenzo[c][l,2,5]oxadiazol-4-yl)amino)ethyl methacrylate(NBDME),red fluorescent dye 9-(diethylamino)-5-oxo-5H-benzo[a]phenoxazin-2-yl methacrylate(NRME)respectively as the energy donor,energy-matched photoswitchable molecule(4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methyl-thiophene-4,2-diyl))bis(methylene)diacrylate(DTEDA)as the energy acceptor,three kinds of photoswitchable fluorescent polymeric nanoparticles were prepared by emulsion polymerization,and three kinds of analogical fluorescent polymer nanoparticles were prepared.Three photo-stable fluorescent polymeric nanoparticles were prepared by EANI,NBDME and NRME,respectively.Then,the reversible regulation of white light to full color in solution and film was achieved by mixing the polymeric nanoparticles with different color fluorescence in a suitable ratio.In addition,the photoswitchable fluorescent polymeric nanoparticles systems have been successfully applied in the frontier fields of data encryption and photocontrolled luminescent device.(2)The monosubstituted 2-(2-(5,6,12,13-tetrachloro-9-(2-(2-((3-(3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indolin]-1'-yl)propanoyl)oxy)ethoxy)ethyl)-1,3,8,10-tetra oxo-9,10-dihydroanthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin-2(1H,3H,8H)-yl)ethoxy)ethyl acrylate(SP-PDI-DA)and di sub stituted(((5,6,12,13-tetrachloro-1,3,8,10-tetraoxoanthra[2,1,9-deg:6,5,10-d'e'f']diisoquinoline-2,9(1H,3H,8H,10H)-diyl)bis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl)bis(3-(3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indolin]-1'-yl)propanoate)(SP-PDI)were synthesized by introducing a photoswitchable spiropyrane unit 3-(3 ',3 '-dimethyl-6-nitrospiro[chromene-2,2'-indolin]-1'-yl)propanoic acid(SP-COOH)with perylenediimide.Moreover,the energy-matched photoswitchable molecule bis(4-(acryloyloxy)butyl)4,4'-(perfluorocyclopent-1-ene-l,2-diyl)bis(5-methylthiophene-2-carboxylate)(DTE-BA)was synthesized.Photoswitchable fluorescent polymeric nanoparticles PDI-SP-DTE and PDI-2SP-DTE were prepared by miniemulsion polymerization with SP-PDI-DA and DTE-BA,SP-PDI and DTE-BA,respectively.By means of FRET mechanism,PDI-SP-DTE and PDI-2SP-DTE can be alternately irradiated by visible light and 365 nm UV,the fluorescence of nanoparticles can be invertiblely switched between green and red.Then,and the nanoparticles can be reversiblely switched between red fluorescence and quenching alternately upon 365 nm UV and 254 nm UV,achieving fluorescence on/off.PDI-SP-DTE and PDI-2SP-DTE can also switch between green fluorescence and quenching under alternating irradiation of visible light and 254 nm UV.The multi-wavelength controlled nanoparticles enables the reversible regulation of multilevel fluorescence switches in both solution and film.In addition,the multilevel photoswitchable fluorescence polymeric nanoparticles system has been successfully applied in logic gates,multilevel data encryption and bioimaging.(3)A polyurethane(PU)combined photoswitchable diarylethene(4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-4,2-diyl))dimethanol(DTE-CH2OH)with good mechanical properties was synthesized via one-pot polycondensation reaction.Compared with the existed photoswitchable materials,the polyurethane(DTE-PU)containing photoswitchable diarylethene has good transparency and mechanical properties,rapid responsiveness,and good fatigue resistance,revealing eminent photoswitchable properties.The DTE-PU has been successfully applied in the fields of controlled photowritable and erasable patterning and information storage.