The fundamental optical storage mechanism of the laser light eddressable azobenzene moiety is briefly introduced.A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenz...The fundamental optical storage mechanism of the laser light eddressable azobenzene moiety is briefly introduced.A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularlyspaced side chains. Thin films of these materials are particularly well suited for holographic storape. Notable figures of meritsof liquid crystalline polyesters are response time to blue-green laser light of the order of nanoseconds, storage capacityexpressed as 5000 lines/mm, and high, permanent (almost nine years) diffraction efficiency of the order of 50% or greater,and erasability, The implications of the main chain nature for polyester morphology and for the permanency of the inducedanisotropy are discussed, The design and methods of preparation of other significantly different polymer scaffolds supportingcyanoazobenzene are elaborated. Oligopeptides always result in amorphous materials, whereas copolymethacrylates anddendritic or hyperbranched polyesters provide some materials that exhibit liquid crystallinity. However, none of these scaffolds affords materials that result in permanent anisotropy when exposed to interfering laser light.展开更多
Photomechanical response of amorphous polymer films containing azobenzene chromophores in side chains is studied. By invoking the trans-cis isomerization mech- anism, the steady-state deformation of the film induced b...Photomechanical response of amorphous polymer films containing azobenzene chromophores in side chains is studied. By invoking the trans-cis isomerization mech- anism, the steady-state deformation of the film induced by uniform illumination of linearly polarized light is obtained analytically. The deformation turns out to be of entropic origin,produced to compensate the entropy decrease due to photo-induced redistribution of azobenzene chromophores normal to the polarization direction. The predicted elongation direction of the film is consistent with previous experimental observations.展开更多
For side-chain liquid-crystalline polymers(SCLCPs)bearing calamitic mesogens,nematic and typical smectic(Sm)phases are expected.Here,using a precise polyethylene derivative with the biphenyl moiety tethered on every n...For side-chain liquid-crystalline polymers(SCLCPs)bearing calamitic mesogens,nematic and typical smectic(Sm)phases are expected.Here,using a precise polyethylene derivative with the biphenyl moiety tethered on every ninth carbon(P9,b),we demonstrated that an SCLCP could form a crystal(Cr)phase in addition to an Sm phase.Two opposing interrelations of main-and side-chains determined the molecular packings.While the side-chain inclined to be perpendicular to the main-chain in the Sm phase,they paralleled and coassembled in the Cr phase with an orthorhombic structure.The Sm phase of P9,b was new in SCLCPs.Within the mesogen sublayers,the biphenyls were tilted and had a type of two-dimensional positional order,making this Sm phase ordering higher than that of smectic C.The Sm phase was metastable and kinetically grew faster below its isotropic temperature.However,it could not convert to the stable Cr phase unless it transitioned into the melting state.Fantastically,P9,b rendered the lamellar crystal in the Cr phase.The lenticular lamellae resembled that found in linear polyethylene crystallized at low undercooling.Importantly,albeit having the large anisotropic pendants situated regularly in the backbone,P9,b could follow the principle of chain-folding crystallization.展开更多
文摘The fundamental optical storage mechanism of the laser light eddressable azobenzene moiety is briefly introduced.A modular and flexible synthesis design furnishes polyester matrices covalently integrating cyanoazobenzene in regularlyspaced side chains. Thin films of these materials are particularly well suited for holographic storape. Notable figures of meritsof liquid crystalline polyesters are response time to blue-green laser light of the order of nanoseconds, storage capacityexpressed as 5000 lines/mm, and high, permanent (almost nine years) diffraction efficiency of the order of 50% or greater,and erasability, The implications of the main chain nature for polyester morphology and for the permanency of the inducedanisotropy are discussed, The design and methods of preparation of other significantly different polymer scaffolds supportingcyanoazobenzene are elaborated. Oligopeptides always result in amorphous materials, whereas copolymethacrylates anddendritic or hyperbranched polyesters provide some materials that exhibit liquid crystallinity. However, none of these scaffolds affords materials that result in permanent anisotropy when exposed to interfering laser light.
基金supported by the National Natural Science Foundation of China (11072231, 11132009)
文摘Photomechanical response of amorphous polymer films containing azobenzene chromophores in side chains is studied. By invoking the trans-cis isomerization mech- anism, the steady-state deformation of the film induced by uniform illumination of linearly polarized light is obtained analytically. The deformation turns out to be of entropic origin,produced to compensate the entropy decrease due to photo-induced redistribution of azobenzene chromophores normal to the polarization direction. The predicted elongation direction of the film is consistent with previous experimental observations.
基金supported by the National Natural Science Foundation of China(grant nos.21634001,21875157,and 51921002)the National Key R&D Program of China(no.2018YFB0703703)The TEM facility is made available by Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices(nos.2019B121203003 and 2016ZT06C322).
文摘For side-chain liquid-crystalline polymers(SCLCPs)bearing calamitic mesogens,nematic and typical smectic(Sm)phases are expected.Here,using a precise polyethylene derivative with the biphenyl moiety tethered on every ninth carbon(P9,b),we demonstrated that an SCLCP could form a crystal(Cr)phase in addition to an Sm phase.Two opposing interrelations of main-and side-chains determined the molecular packings.While the side-chain inclined to be perpendicular to the main-chain in the Sm phase,they paralleled and coassembled in the Cr phase with an orthorhombic structure.The Sm phase of P9,b was new in SCLCPs.Within the mesogen sublayers,the biphenyls were tilted and had a type of two-dimensional positional order,making this Sm phase ordering higher than that of smectic C.The Sm phase was metastable and kinetically grew faster below its isotropic temperature.However,it could not convert to the stable Cr phase unless it transitioned into the melting state.Fantastically,P9,b rendered the lamellar crystal in the Cr phase.The lenticular lamellae resembled that found in linear polyethylene crystallized at low undercooling.Importantly,albeit having the large anisotropic pendants situated regularly in the backbone,P9,b could follow the principle of chain-folding crystallization.