The direct optical switching of bistable cholesteric textures (i.e., planar and focal conic textures) in chiral azobenzene-doped liquid crystals (LCs) is demonstrated. Chiral azobenzene is a chiral dopant with optically tuned helical twisting power that results from the photo-isomerization between trans- and cis- isomers via exposure to UV or visible light. The pitch length of the material can be optically and repeatedly elongated and shortened. With regard to free energy, LCs tend to be stable at planar (focal conic) textures when pitch length is elongated (shortened) by exposure to UV (visible) light. Thus, direct optical switchable LC displays are investigated.
Two mononuclear nonheme Fe(III) complexes, [PPh4][Fe(III)(PS3″)(OCH3)] (1) and [PPh4][Fe(III)(PS3″)(Cl)] (2), supported by a tris(benzenethiolato)phosphine derivative PS3″ (PS3″ = P(C6H3-3-Me3Si-2-S)3(3-)) have been synthesized and characterized. The structures resolved from X-ray crystallography show that Fe(III) centers in both complexes adopt distorted trigonal-bipyramidal geometry with a methoxide or a chloride binding in the axial position. The magnetic data for both are consistent with intermediate-spin Fe(III) centers with a C3 symmetry (S = 3/2 ground state). The bound methoxide in 1 is labile and can be replaced by a CH3CN molecule. The forming Fe(III)-CH3CN species can be further reduced by cobaltcene quantitatively to a stable Fe(II)-CH3CN complex, [Fe(PS3″)(CH3CN)](-). One-electron oxidation of 2 by ferrocenium gave a Fe(IV) analogue, [Fe(IV)(PS3″)(Cl)]. Importantly, the Fe(III)-OCH3 moiety in complex 1 acts as a strong nucleophile that activates the C-Cl bond in CH2Cl2, leading to the formation of complex 2 quantitatively. Complex 1 also reacts with other electrophiles, benzyl chloride and benzyl bromide, to generate Fe(III)-X species (X = Cl or Br). The reactions were investigated and monitored by UV-vis-NIR, NMR, and ESI-MS spectroscopies.
A V(III) complex bearing a tris(thiolato)phoshine derivative mediates the reduction of nitrite without the assistance of external protons or oxophilic substrates. The metal site plays dual roles for the nitrite...
Bistable cholesteric textures (i.e., planar and focal conic textures) in chiral azobenzene-doped liquid crystals (LCs) is demonstrated. Chiral azobenzene is a chiral dopant with optically tuned helical twisting power that results from the photo-isomerization between trans-and cisisomers via exposure to UV or visible light. The pitch length of the material can be optically and repeatedly elongated and shortened. With regard to free energy, LCs tend to be stable at planar (focal conic) textures when pitch length is elongated (shortened) by exposure to UV (visible) light. Thus, direct optical switchable LC displays are investigated.
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