Masuki Kawamoto

Non-destructive erasable molecular switches and memory using light-driven twisting motions

Novel types of chiroptical switches and memory with non-destructive readout that are entirely optically controlled for molecular devices in solution and neat films.

Planar chirality of twisted trans-azobenzene structure induced by chiral transfer from binaphthyls.

The absolute configuration of a binaphthyl-azobenzene dyad 2b, which has a chiral axis and a chiral plane, was determined by comparing the experimental circular dichroism (CD) spectra with the theoretical CD spectra calculated by the time-dependent (TD)-DFT method. The CD signals of the trans-azobenzene moiety indicated that the two benzene rings of this moiety are twisted unidirectionally. It is suggested that these dyads with shorter linkers may be suitable for use as chiroptical switches.

Photoinversion of cisoid/transoid binaphthyls.

Axially chiral binaphthyl-azobenzene cyclic dyads in which the two moieties are connected by two linkers of different lengths were synthesized. In the case of benzylated-binaphthyl analogue 2b, photoirradiation resulted in a dramatic change of the CD spectrum and optical rotation. Experimental and theoretical analyses indicated that the dihedral angle of the two naphthalene rings is strongly coupled to the azobenzene photoisomerization; cis-azobenzene induces a transoid-binaphthyl structure, while trans-azobenzene induces a cisoid-binaphthyl structure.

Polarized emission from self-organized low-molecular-weight liquid crystals with the aid of hole-injecting materials

Electroluminescent (EL) properties of a low-molecular-weight liquid crystal (LC), which is composed of an oxadiazole moiety as an electron-transporting unit and an amine moiety as a hole-transporting unit, were investigated. The most significant characteristic of the LC is to possess bipolar carrier-transporting abilities. The bipolar LC makes it possible to fabricate a simple EL device. We fabricated an EL device (cell gap: 2 μm) with configuration of indium tin oxide (ITO)/LC/MgAg. The device emitted visible light at above 10 V. In particular, the values of luminance and current density of an EL device containing poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT) as a hole-injecting layer were ten and six times higher than those of the ITO/LC/MgAg device without the PEDOT layer, respectively. Furthermore, surfaces of the glass substrate with an ITO electrode and a PEDOT layer were rubbed to align mesogens. Dichroic ratio of the emission from an ITO/rubbed PEDOT/LC/MgAg device was estima...

Synthesis and Conformation of Substituted Chiral Binaphthyl- Azobenzene Cyclic Dyads with Chiroptical Switching Capabilities

Optically active binaphthyl-azobenezene cyclic dyads were synthesized to develop a photochromic switching molecule. Azobenezene moieties were cis-trans isomerized by photoirradiation. As a reflection of the structural change, the specific optical rotation and circular dichroism underwent significant shifts. Under certain conditions, the positive-negative and zero-positive (or zero-negative) signals were reversed. Optical rotation may potentially be applied in noise-cancelling nondestructive photoswiches. The conformations were studied by experimental and theoretical methods. The results revealed that the helical chirality, (P) or (M), of the cis-azobenzene moiety was induced by intramolecular axial chirality. The twist direction depended on the axial chirality as well as the azobenzene linkage position to the binaphthyls, but was independent of the identity of substituted groups. 2,2’-Linked-(R)-binaphthyl was found to induce cis-(P)-azobenzene, whereas symmetrically 7,7’-linked-(R)-binaphthyl was found to induce cis-(M)-azobenzene.

Photoinduced Control over the Self-Organized Orientation of Amorphous Molecular Materials Using Polarized Light

Novel chiral amorphous molecular materials containing photoresponsive azobenzene moieties were designed and synthesized. These materials led to the formation of smooth and uniform thin films without grain boundaries. Photoirradiation of the thin film with linearly and elliptically polarized light caused trans-cis photoisomerization of the azobenzene moieties and resulted in an anisotropic orientation of the materials. Maximum change in a value of birefringence, Deltan, after irradiation of the linearly polarized light is about 0.08 with a response time of 10 s. However, when irradiation was ceased after photoinduced orientation, the value of Deltan decreased due to relaxation of the azobenzene moieties. Furthermore, these materials exhibited a high efficiency of a photoinduced polarization rotation over 30 deg mum(-1) after irradiation with the elliptically polarized light for 60 s. We also found that the efficiency depends on ellipticity of the incident light and on the thickness of the sample. The origin of the large change in the molecular orientation is the anisotropic arrangement of the azobenzenes in the terminal groups upon irradiation with the linearly and elliptically polarized light.

Light-driven twisting behaviour of chiral cyclic compounds

Chiral cyclic compounds exhibited light-driven twisting by means of trans-cis photoisomerization in 1,4-dioxane solution, a neat film, and a liquid-crystalline host.

Fusion of photochromic reaction and synthetic reaction: Photoassisted cyclization to highly strained chiral azobenzenophanes

A method for synthesizing highly strained cyclic structures by combining photochromic and synthetic reactions is described. Tightly linked azobenzene-binaphthyl dyads (R)-4 and (R)-6 could not be obtained by conventional cyclization, but continuous application of photoirradiation, which induced (E)→(Z) isomerization of the azobenzene moiety, allowed the cyclization reaction to proceed, affording the desired chiral azobenzenophanes.

White emission from liquid-crystalline copolymers containing oxadiazole moieties in the side chain

A liquid-crystalline polymer in the side chain was synthesized through copolymerization of a bipolar carrier-transporting monomer with a liquid-crystalline monomer containing oxadiazole moieties substituted with trifluoromethyl groups. A single-layer light-emitting diode of indium tin oxide (ITO)/copolymer/MgAg emitted white light with a maximum luminous efficiency of 0.1cd∕A. The origin of the white emission in the copolymer is the electroplex between bipolar carrier-transporting moieties and strong electron-withdrawing moieties. Furthermore, a simple multilayer device with configuration of ITO/poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid)/copolymer/MgAg device showed white emission with CIE 1931 chromaticity coordinates (x,y): (0.30, 0.33).

Mass migration on a polymer surface caused by photoinduced molecular rotation

We demonstrated the formation of a photoinduced surface relief grating using thin films comprising a photochromic molecular motor, 9-(2-phenyl-2,3-dihydro-cyclopenta[a]naphthalen-1-ylidene)-9H-fluorene. Results show that mass migration occurred by patterned light irradiation prepared from interfered laser beams and a photomask.