Search Results (4)

Photoisomerizable molecules in liquid crystals (LCs) allow for photoinduced phase transitions, facilitating applications in a wide variety of photoresponsive materials. In contrast to the widely investigated azobenzene structure, research on the photoinduced phase-transition behavior of imine-based LCs is considerably limited. We herein report the thermal and photoinduced phase-transition behaviors of photoisomerizable imine-based LC dimers with twist–bend nematic (N_TB) phases. We synthesize two homologous series of ester- and thioether-linked N-(4-cyanobenzylidene)aniline-based bent-shaped LC dimers with an even number of carbon atoms (n = 2, 4, 6, 8, and 10) in the central alkylene spacers, namely, CBCOOnSBA(CN) and CBOCOnSBA(CN), possessing oppositely directed ester linkages, C=OO and OC=O, respectively. Their thermal phase-transition behavior is examined using polarizing optical microscopy and differential scanning calorimetry. All dimers form a monotropic N_TB phase below the temperature of the conventional nematic (N) phase upon cooling. Remarkably, the N_TB phases of CBCOOnSBA(CN) (n = 2, 4, 6, and 8) and CBOCOnSBA(CN) (n = 6 and 8) supercool to room temperature and vitrify without crystallization. In addition, the phase-transition temperatures and entropy changes of CBCOOnSBA(CN) are lower than those of CBOCOnSBA(CN) at the same n. Under UV light irradiation, the N_TB and N phases transition to the N and isotropic phases, respectively, and reversibly return to their initial LC phases when the UV light is turned off. Full article

The well-known effect of bending of acicular crystals undergoing photochemical reactions is associated with the transformation gradient across the crystal thickness caused by the absorption of light. It is believed that the direction of bending is unambiguously dictated by the sign of the axial component of the reaction strain and due to the higher light intensity on the irradiated side of the crystal. In this study, it is shown experimentally and theoretically that thin crystals with a convex irradiated surface bend in the opposite direction if their thickness is less than the light penetration depth. The reversal of the bending direction is due to the lens effect, able to overcome the absorption of light in a thin crystal and provide a higher light intensity on the rear side of the crystal. A crystal of [Co(NO₃)₅NO₂]Cl(NO₃) experiencing nitro-nitrito photoisomerization, begins to bend in the opposite direction after it is thinned by etching to 2 µm when irradiated at the wavelengths of 523 nm, 465 nm, and 403 nm, absorbed at a depth of more than 10 µm in the crystal, but bends in the normal direction under 350 nm light absorbed at a depth of about 1 µm. The experimental results are fully confirmed by modeling the interaction of plane EM wave with crystals of various cross sections. Full article

In this work, photomechanical molecular crystals of 4-(4-(6-Hydroxyhexyloxy) phenylazo) pyridine (6cazpy) and its zinc(II) organic complex (complex-I) were synthesized and crystallized. DSC and TGA were used to characterize and compare properties of 6cazpy and its complex-I crystals. Photoinduced motions of 6cazpy crystals and its complex-I crystals were investigated and compared by UV/Vis irradiation. Bending away motions from the light source were observed from both 6cazpy crystals and its complex-I crystals. The bending away motion was attributed to the trans-to-cis photoisomerization of azopyridine derivatives in the crystalline phase. It is worth noting that the photomechanical properties of complex-I were enhanced by the formation of the ligand, which might be caused by the looser packing of molecules inside complex-I crystal. In addition, because of the existence of ligand, which combined two photoactive groups in each complex-I molecule, the isomerization reactions of these two photoactive groups in the molecules can increase the photomechanical movement ability of the crystal. It was also found that the crystal size and shape will affect the photoinduced movement of the crystals. PXRD and AFM were used to investigate the molecular mechanism and the surface topological change upon photoisomerization. The corresponding mechanism was proposed. Full article

We investigated photoinduced crystal bending behavior of various photochromic diarylethenes. In all the diarylethene derivatives we used in this work, the relationship between the initial photoinduced bending speed and the crystal thickness was well explained by the easy-handled Timoshenkoʼs bimetal model. Moreover, we proposed a quantitative analysis method to reveal the relationship between the bending speed and the molecular structure of diarylethenes. These results provide the quantitative evaluation method of the photoinduced crystal bending speed. Full article