Emission stimulated with friction or pressure is called as triboluminescence (TL). TL has a long history but few reports have been reported because of the difficulty of application and analysis of basic properties. We discovered some imide compounds not having symmetric center showed TL and studied relationship between the molecular structures and TL properties.

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Organic light-emitting diodes (OLEDs) based on luminescent heavy metal complexes are playing a key role in next generation flat panel displays and solid-state lightings based on OLED technology, Development of highly luminescent deep blue phosphorescent materials with CIE coordinates less than (0.20,0.20) are desired. Now we synthesized novel platinum complexes having an electron-accepting phenylsulfonyl group. We also investigated the physical properties.

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Dehydrobenzoannulenes (DBAs) are cyclic conjugated systems involving benzene rings and acetylene units. Due to their rigid frameworks with rich π electrons, DBA derivatives are adapted as building blocks of supramolecular assemblies. Recently, we reported that a boomerang-shaped [12]DBA derivative possessing two methyl ester groups in syn positions successfully formed organogels in various organic solvents. Inspired by this result, we designed and synthesized a [14]DBA derivative which possesses two methyl ester moieties in syn positions. [14]DBA derivative was revealed to yield polymorphic crystals which showed different luminescent colors even though the crystals were composed of an identical molecule.

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Recently, we found that 17,17-dialkyltetrabenzofluorenes (dialkylTBF) exhibit considerably high fluorescent quantum yields in solution and the solid states. Although various TBF derivatives have been known for a long time, no derivatives bearing substituents on the aromatic rings have been prepared so far. Recently, we found that treatment of dialkylTBFs with excess amount of NBS in a DMF solution afforded 3,14-dibromo derivatives in good yields with high selectivity. A variety of TBF derivatives bearing substituents at 3,14-positions were synthesized using the Sonogashira and Suzuki couplings from the dibromides as versatile synthetic building blocks. We have investigated their physical and fluorescent properties.

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Aromatic-aromatic interactions play an important role in a variety of chemical and biological processes. Interactions within benzene dimers are well documented for a series of aromatic clusters. In contrast, because of difficulty in isolation of artificial model system, investigations on high-order aromatic clusters are largely limited. Now, we have studied the substituent effects of benzene trimer interactions by using trimer complexes of Zn (II) N-confused porphyrins (NCP). 5-Aryl NCP zinc complexes form a self-assembled trimer in chloroform, and exist as a mixture of monomer and trimer in pyridine. From the equilibrium constant between trimer and monomer, which was determined by ¹H NMR method, and van't Hoff plot, we obtained the stabilization energies of aromatic ring trimers. The stabilization energies of aromatic ring trimer interactions largely decreased when the electron drawing groups were substituted on benzene ring.

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Chiral separation of Möbius aromatic Pd, Ni, and Pt complexes of [28]hexaphyrin(1.1.1.1.1.1) was achieved by chiral HPLC. The absolute configuration for the Pd complex was determined by X-ray crystal analysis and the racemization activation energy was estimated to be 127.2 kJ/mol for the Pd complex. Asymmetric metallation of hexaphyrin was achieved by using BINAP-Pd(II) salt in 23% ee. This is the first example for asymmetric synthesis of Möbius twisted molecule.

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The first synthesis of noncoordinating meso-aryl-subporphyrin cation was achieved by the reaction of methoxo-5,10,15-triphenylsubporphyrinateboron(III) and hexabromocarborane triethylsilylium complex in toluene at room temperature for 3 hours. The cation complex was fully characterized by ¹H NMR, ¹¹B NMR, ESI-TOF MS spectroscopy and X-ray diffraction analysis. The solid state structure of subporphyrin cation exhibits planar conformation, which is sharply contrasted with the bowl-shaped structure of neutral boron-methoxy substituted subporphyrins.

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We've already reported porphyrin pincer complexes with various metals. Here we'll report newly the synthesis and properties of porphyrin pincer platinum complex. We'll report also the synthsis and properties of p-ethynylbenzene bridged porphyrin pincer platinum complex dimer.

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Highly stable eta2-porphyrin Ru pi-complexes have been synthesized. The formation of the eta2-pi-bond has been facilitated through pi-pi stacking interaction between the porphyrin and the planar ligand on Ru. pi-Coordination of ruthenium to porphyrin results in dramatic changes in aromaticity and electronic properties. These properties are controllable via a fine-tuning of a ligand on ruthenium.

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A variety of phthalocyanine (Pc) dimers have been reported including both double-decker and co-planar type compounds and their spectroscopic and electrochemical properties have been shown to differ significantly from those of the corresponding monomers. However, control of three-dimensional arrangement of Pc units in dimer systems has been rather limited although such Pc dimers and oligomers are potentially useful as novel Pc-based functional materials. In order to control three-dimensional arrangement of Pc units in dimer systems, we used a biphenyl group as a linker unit, which led to novel three-dimensionally controlled dimers molecule bearing a propeller-like conformation of Pc units due to the dihedral angle of the biphenyl unit. The target Pc dimers were synthesized by a mixed macrocyclization reaction of a biphenyl linked phthalonitrile which was prepared by reacting of 4-brono-5-nitrophthalonitrile with 2,2',6,6'-tetrahydroxybiphenyl and the absolute structure was determined by chiral resolution and X-ray crystallography. No racemization was occurred during the reactions, and the obtained chiral dimers exhibit strong Cotton effect with mirror-imaged circular dichroism (CD) signals. In this presentation, we report synthesis and spectroscopic properties of the Pc dimers including magnetic circular dichroism (MCD) spectra and theoretical calculations.

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A mixed-condensation reaction of 1,8-dicyanonaphthalene and phthalonitrile provided a novel subphthalocyanine analogue bearing a six-membered ring. This analogue retained the 14pi aromatic characteristics of subphthalocyanine, and spectroscopic and electrochemical properties were largely altered. In this report, sysnthesis, X-ray analysis, absorption and MCD spectra, and electrochemical results will be presented with the assistance of theoretical calculations.

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To the best of our knowledge, the D_2d-C₈₄ (23) cage is the only case that isolated empty fullerene and endohedral metallofullerene have same cage structure. Therefore,D_2d-C₈₄ (23) and Sc₂C₂@ D_2d-C₈₄ are attracted special interest as they allow a comparison between the empty fullerene and endohedral metallofullerene with the same cage structure. We report here the chemical functionalization and the difference of reactivity of D_2d-C₈₄ (23) and Sc₂C₂@ D_2d-C₈₄ against adamantylidene carbene.

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The [60]fullerene pentadduct bearing perfluoroalkyl chains forms a stable bilayer vesicle in water and the perfluoroalkyl chains expose an aqueous phase. In this study, we found that the fullerene bilayer vesicle could be modified easily by using fluorous interaction between a fluorous environment of the fullerene vesicle surface and a fluorous tagged saccharide. Concretely, the mannose with a perfluorooctyl chain incorporated into the vesicle surface only by mixing these aqueous solutions. We revealed that the interaction between the vesicle and concanavalin A, which is a well studied lectin with a specific interaction with mannose, increased by the surface modification of the vesicle with mannose.

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In order to clarify the structure-function relationship of carotenoids bound to LH1 antenna pigment-protein complex from purple photosynthetic bacteria, we performed the re-association experiments using a synthetic carotenoid analogue, 3,4-dihydroanhydrorhodovibrin. Spectroscopic properties and energy transfer efficiency from carotenoid to BChl a are described.

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The oxidation of organic compounds sometimes accompanies considerable geometrical change when compared to their neutral states. Photochemical electron transfer reactions provide a good tool to investigate such system. We have previously shown that phenothiazine trimer radical cation exhibits a strong intramolecular CT band because of its unique structure. When the phenothiazine trimer framework is incorporated in an intramolecular electron transfer system, the initially formed radical ion pair as well as the geometrically relaxed radical ion may be observed. In this presentation, we report photo-induced electron transfer reactions of (phenothiazine monomer and phenothiazine trimer)-anthraquinone dyad bridged by bicycle[2.2.2]octane.

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Recently, "Molecular electronics" which intends to construct electronic device by single molecule instead of traditional silicon semi-conductor receives much attention. Our purpose is to fabricate a device which changes the conductance by photoinduced electron transfer (PET) from donor molecule to acceptor molecule. For this purpose, dinitrobenzene derivative was synthesized as acceptor molecule and oligothiophenedithioacetyl was synthesized as donor molecule. Optical and electrochemical property for both molecules was examined. Then the gold nanoparticles covered by acceptor molecules were synthesized and the gold nanoparticles were bridged by donor molecules to form network between interdigitated gold electrodes. The change of the conductance of the network upon photoirradiation induced by PET will be reported.

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Pillar[5]arene, which is para-bridged macrocycle, forms racemic crystal by X-ray single crystal structural analysis. In this work, to obtain the enantiomerically pure chiral pillar[5]arene, we synthesized pillar[5]arene derivatives having 2S-methylbutoxy groups at both rims (S-pillar[5]arene). From the result of CD spectra, no CD effects were observed in S-monomer. On the other hand, the CD effects were found in S-pillar[5]arene. Thus, it is obvious that S-pillar[5]arene is shows planar chirality.

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Water-soluble pillar[5]arene was synthesized by introduction of carboxylate anions at both upper and lower rims. When cationic viologen salt was mixed with the water-soluble pillar[5]arene in aqueous media, formation of the stable 1:1 host-guest complex took place. The complexation of the water-soluble pillar[5]arene with the viologen salt lowered the conformational freedom of the cavity.

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Monoalkoxylated calix[4]arenes were synthesized to include lithium ion selectively.
Extraction of alkali metal ion or alkali earth metal ion from the aqueous solution was examined by using the compounds. The metal ion inclusion ability and selectivity was measured by ICPES. And we observed lithium ion inclusion ability of the compounds.

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We have been studying on the thermal responsive self-assemblies for the small-size organic compounds, 1, 3, 5-triureabenzene derivatives, with amphiphilic side chains, showing the lower critical solution temperature (LCST) phenomena and the hydrogellation in aqueous solutions. This time, in order to construct the organic nanoparticles carrying an organic spin , the TEMPO radical was incorporated into 1, 3, 5-triureabenzene derivatives with amphiphilic side chains. The self-assembly behaviors for the obtained TEMPO-triureabenzene derivatives were investigated by VT-UV-vis, VT-¹H-NMR and EPR spectrometries. The size and structures for the organic nanoparticles were determined by DLS and TEM measurements. The relationships between the self-assembly behaviors and the magnetic properties will be discussed in detail.

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Solid-state chiral helical columnar organic fluorophores having a pai-conjugated phenylene ethynylene unit are prepared by using 4-[2-(4-methylphenyl)ethynyl]-benzoic acid and (R)-1-(4-methoxyphenyl)ethylamine [or (R)-1-(4-methylphenyl)ethylamine]. Such chiral pai-conjugated organic fluorophores exhibit fluorescence property in the solid state.

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By using rac-10,10'-dihydroxy-9,9'-biphenanthryl as an electron donor and 2,5-disubstituted-1,4-benzoquinone as an electron acceptor, a colored charge-transfer (CT) host complex is formed. This CT host complex can include aromatic molecules as guests, and the color of this CT host complex changes with the type of guest molecules included. Moreover, the color of the inclusion CT complex can be also tuned by changing the type of the component 2,5-disubstituted-1,4-benzoquinone.

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We synthesized 2,7-diborylanthracene by Miyaura-Ishiyama diborylation as a building block for the construction of .pi.-extended macrocyclic molecules. By using 2,7-diborylanthracene, we synthesized 2,7-di(4-pyridyl)anthracene, 2,7-ditriflateanthracene, 2,7-diethynylanthracene, and so on. Furthermore, we constructed [3+3] cyclic self-assembly of 2,7-di(4-pyridyl)anthracene and Pd(II) based on coordination bonds.

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Previously, we found the tris-urea compound gelled four chloroalkane (CHCl₃, CH₂Cl₂, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane) by different condition. In this research, we synthesized some types of derivatives. Their assembling behaviors were different from the slight alteration of the structure.

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Proteins were separated by polyacryamide gel electrophoresis based on difference of molecular weight and/or isoelectic point. Observation of specific segregation pattern would be expected by using supramolecular hydrogel for electrophoresis. We aimed to establish a supramolecular hydrogel electrophoresis with specific separation of proteins. We synthesized a low molecular weight hydrogelator that introduced sugar into tris-urea and examined separation ability of proteins by supramolecular hydrogel electrophoresis.

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We report the syntheses of the 2'-deoxyguanosine derivatives with tetrathiafulvalene (TTF) moieties for a construction of electrically conductive supramolecule. An intermolecular hydrogen-bond network was confirmed by ¹H NMR and NOESY spectra. The strong hydrogen-bond network enables formation of flexible self-supporting films. The composite film of the derivatives and Tetracyanoquinodimethane (TCNQ) exhibits electrically conducting property (3.7 x 10^-2 Scm^-1).

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Molecular capsules which provide precise internal spaces have been created as the active site of the artificial enzyme. In this study, a zinc(II)-included hemicryptophane, which has a zinc(II) centre embedded in the cavity, was synthesized in high yield and characterized by ESI-MS, NMR spectroscopy, and X-ray crystal structure analysis. The X-ray crystal structure shows that zinc(II)-included hemicryptophane has a pre-organized cavity, formed by the cyclotriveratrylene (CTV) and tris(aminoethyl)amine (tren) moieties.

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Macrocycles having preorganized, defined cavities and structures of molecular dimensions have attracted great interest because of promising applications toward extended pai-conjugated systems or tube-like structures by self-assembly. Here we report the preparation, X-ray structures and spectroscopic properties of hydrindacene-based macrocycles. These macrocycles are endowed dimensionally ordered array of functionalities in both horizontal and vertical directions of the macrocyclic backbone, because multi-dimensional modification is possible in the hydrindacene unit. Through Eglington coupling of the diethynyl hydrindacenes, we prepared macrocycles 2-4 consisting of 2-4 units of hydrindacene, which have methoxy, bromo, thienyl or styryl substituents. We will discuss the electric interaction among hydrindacene units based on the UV/vis and fluorescent spectra and cyclic voltammogram.

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We have designed a novel allosteric receptor by connecting two hydrindacene units with a spacer unit working as a rotational axle. We expected that this receptor would show a positive homotropic allosteric binding ability toward two guest molecules due to the rotational restriction of hydrindacene units upon binding with the first guest. In addition, the introduction of asymmetric centers at 2, 6 positions of each hydrindacene units could lead to a novel allosteric receptor with a chiral molecular recognition ability. We report here the preparation, spectroscopic and binding properties of a chiral di(4-hydrindacenyl)acetylene.

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We previously reported successful application of hydrindacenediamide receptor toward cooperative supramolecular polymerization driven by the positive allosteric binding. The initial dimerization of the monomer molecule, which consists of the receptor and two pendant resorcinol units, activates the receptor units for the subsequent monomer bindings by the inherent allosteric effect. This would lead to the formation of cooperative supramolecular polymers. Herein, we prepared monomers with linkers and ester side chains of various lengths to investigate structural effects on cooperativity and binding manner in supramolecular porymerizations. The dilution experiments and VT-NMR of a series of monomer solution showed the similar supramolecular polymerizations in all monomers, whereas only the monomers with short linkers gelated several aromatic solvents.

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We previously reported that the hydrindacenehexaamide receptor shows an excellent assembly capability for resorcinols. We report here our attempts to construct novel macrocycle host molecules by structural modification of hydrindacenehexaamide receptor. We prepared receptor building block that has formyl groups working as a connecting group at 2, 6-positions of hydrindacene unit. We are now preparing novel macrocycles consisting of several the hydrindecene receptors and diamino-spacer units by forming linking imine bonds.

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A new double helicate having two spiroborate moieties was prepared from an ortho-linked oligophenol with a bipyridine unit and NaBH₄. The X-ray single crystallography analysis revealed that the helicate adopted a double helical structure, in which the two Na cations were chelated by the bipyridine units. The 1D and 2D ¹H NMR spectra indicated that the double helical structure was also retained in solution. Moreover, the helicate was resolved into the two enantiomers by use of chiral HPLC, as evidenced by their distinct CD spectra that were mirror image to each other.

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We have reported the first complementary double helices, of which each strand consists of crescent-shaped m-terphenyl groups bearing chiral amidines and/or achiral carboxylic acids. In this study, we designed and synthesized a novel double helix formed from the boronate ester and diol strands via the ester transfer reaction. (48 words)

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Oligoaniline bearing L-alanine chains (-L Ala-OMe) was designed as a unit molecule of π-conjugated polymer, polyaniline. The ¹H NMR and FT-IR spectra showed the presence of intramolecular hydrogen bonds. The oligoaniline exhibited an induced circular dichroism (ICD), which appeared at the absorbance region of the phenylenediamine π-conjugated moiety, indicating the chirality-organized structure. The crystal structure of the phenylenediamine derivative revealed the formation of intramolecular hydrogen bonds, which was found to play an important role in structural regulation of the phenylenediamine moiety.

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Dehydrobenzo[12]annulene (DBA) derivatives are attractive molecules as building block cores of supramolecular assemblies, which are expected to exhibit optical and/or electrical functionality. In connective with this, we performed construction of crystalline supramelecular assemblies with inclusion space by using C₃ symmetric DBA derivatives with polyaromatic substitutes. As a result, the crystals with one-dimensional inclusion space around the stacked DBA molecules were obtained. We report the detail of the crystal structures and structural conversion of the DBA assemblies through guest molecules desorption and insertion.

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Cyano-bis(biphenyl)ethene derivative, which exhibits aggregate-induced enhanced emission character was fixed to [2,2]-paracyclophane and its fluorescence behavior was compared to the corresponding isolated monomer in a solution state. Synthesis was performed using Suzuki coupling reaction of dibromo-[2,2]-paracyclophane with boronic acid derivative. The fluorescence quantum yield and the emission lifetime ware measured. 2.6-fold fluorescence enhancement was observed in the fixed pseudo-para derivative. The fluorescence rate constant and non-radiative rate constant ware calculated. Non-radiative rate constant was similar in these two derivatives but the fluorescence rate constant was increased in the fixed derivative. Therefore, the fluorescence rate constant was suggested to be the main factor.

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Recently, we have reported that two molecule of cavitand tetraboronic acid and four molecule of bis(catechol)-linker self-assemble into a boronic ester cavitand-capsule. Here, we describe the encapsulation of 2,6-diacetoxy-9,10-bis(p-tolylethynyl)anthracene in the capsule and the photochemical properties and stability of this guest@capsule.

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We prepared stimulus responsible gel consisting of bifunctional boronic acid monomer and diol compounds that constructed a reversible covalent bond.We synthesized diboronic acid with azobenzene moiety showing photoisomerization.When the boronic acid and polyvinyl alcohol were mixed, the gel was obtained. The gel was converted to sol showing fluidity after UV-vis photo irradiation. The sol was reconverted to the gel showing not fluidity after photo irradiation.We found that the gel indicates sol-gel phase transition by photo stimuli.

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We report here that the geminal bond participation in the Carroll rearrangement. The electronic structure at the transition state (TS)of the model reaction was subjected to the bond model analysis, which showed that the interaction to the geminal bond at the Z-position greatly stabilized the TS. Therefore, We can predict that the substituent with the more electron-donating sigma-bond should prefer to occupy the Z-position of the product. We designed the alkyl- and silyl-substituted substrates. The Z-selectivity was confirmed by the theoretical calculations and the experoments. Substitution of the silicon atom to a germanium should enhance the selectivity, which was also confirmed by the calculations and the experiments.

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Reduction of nitroaromatics was carried out by the photoinduced electron transfer reaction from Ru(bpy)₃²⁺, using EDTA as a sacrificial donor and methyl viologen (MV²⁺) as an electron mediator. Ten minutes irradiation of 50% aq. MeCN solution containing Ru(bpy)₃²⁺, MV²⁺ and EDTA resulted in 0.2 mM MV^+· accumulation, while the addition of 0.1 mM m-COCF₃-PhNO₂ to the solution inhibited the MV^+· accumulation for initial 10 min irradiation. The subsequent irradiation, however, afforded MV^+· as much as in the absence of m-COCF₃-PhNO₂. The suppression period of MV^+· accumulation was shortened to 5 min when p-F-PhNO₂ was added to the solution instead. The product analysis of the photoreaction by the aid of ¹⁹F NMR spectroscopy revealed either photoreaction of m-COCF₃-PhNO₂ or p-F-PhNO₂ proceeded by the successive two-electron reductions of nitro group affording ArNO and ArNHOH as intermediates to give ArNH₂ as a final product.

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The substituent effects on the acetolysis of α-CF₃-phenylethyl triflate (1) and β-CF₃-phenylethyl nosylate (2) were analyzed with LArSR equation, resulting ρ=-3.43, r⁺=0.67 and ρ=-3.20, r⁺=0.75, respectively. These exalted r⁺ values compared to that for the k_Δ acetolysis of 2-phenylethyl tosylate (r⁺=0.63) is considered due to the destabilization of the positive charge in the transition state by the adjacent α- or β-CF₃ group. The r⁺ value for the acetolysis of 1, however, is smaller than that for the acetolysis of 2 in spite of the stronger destabilization of positive charge in the transition state of the acetolysis of 1 by the α-CF₃ group. The differences in the r⁺ value is considered to be resulted from the difference in the transition state structures of the two k_Δ acetolyses.

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In this work, we studied photoreaction of new compound 1-3 which consists of a 1-cyano-2-methylnaphthalene (acceptor) and a 2-butene or an anethol (donor) tethered at 2-position of the 1-cyano-2-methylnaphthalene by an alanine peptide chain. Irradiation of a CH₂Cl₂ solution containing 1, with a high-pressure mercury lamp through a Pyrex filter (>280 nm) under argon atmosphere, gave a 1-cyano-2-methylnaphthalene 4. On the other hand, irradiation of the compound 3 resulted in trans-cis isomerization at the anethol moiety.

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The scan calculations with DFT methods were carried out for the parent and dianisyl derivatives of methylenecyclobutanone radical cation. It is suggested that 2,2-dianisyl-3,3-dimethylcyclobutanone radical cation cleaves in the C2-C3 bond, while the C1-C2 bond cleavage is basically favorable to the parent methylenecyclobutanone radical cation.

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It is difficult to study the photochemical reaction of biradicals, because the open-shell molecules are usually unstable and short-lived. However, if one can understand the reaction process, the new chemical reaction may be discovered. In this study, we investigated the generation of some biradicals, including TMM derivatives and cyclopentane-1,3-diyls, and their reactivities in a gas-matrix at 10 K.

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The biradical formed in the reactions of conjugated dienes with triplet excited state carbonyl compounds possesses two resonance forms, 1,4-biradical and 1,6-biradical. It is well known that the 1,4-cyclization reaction affords oxetanes. However, there is no report on the 1,6-cyclization reactions, which affords 1,7-dioxabicyclo[2.2.1]heptane derivatives. In this study, we designed an intramolecular reaction of furan derivatives to prove the 1,6-cyclization reaction.

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The reaction of phenacyl chloride and methoxide ion in dry methanol gave an acetal derivative, which means that the mechanism of this reaction involves an epoxide intermediate. The reaction also gave an ether derivative, and the ratio of these two products was changed with substitution. The reaction mechanism is discussed in detail on the basis of the variation of the product ratio with substituent and the fraction of reaction.

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Two mechanisms are expected for the reaction alpha-haloketones with a nucleophile. In this study, the borderline nucleophilic addition/ substitution reaction of alpha-bromoketones with hydroxide ion is investigated by molecular orbital calculations. Normally, the substitution and addition reactions have different TSs. For the reactions of alpha-bromoacetophenones and hydroxide ion, however, only one transition structure was obtained. In addition, IRC pathway changed from substitution to addition reaction with introducing electron-withdrawing group on the phenyl group.

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For solvolysis, it is believed that nucleophilic solvent assistance (NSA) and electrophilic solvent assistance (ESA) play important roles. MD simulations for hydrolysis of t-BuCl in water solvent were carried out by using FMO-MD and blue moon methods. The calculated free energy profile showed that a transition state (TS) corresponding to heterolysis of C-Cl bond and a contacted ion pair (CIP) were found at the C-Cl distance of 2.8 and 2.9 angstrom, respectively. The evaluated free energy changes for TS and CIP were 14.6, 14.5 kcal/mol. The effect of NSA and ESA was estimated quantitatively.

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Hydroboration of H-Bpin to ynamines was examined in the presence of Schwartz's reagent to give olefinic compounds which carried both heterocyclic amine and boronic ester. Increasement of bond order between corbon and nitrogen atoms were recognized judged by restricted rotation observed in 13C NMR spectra.

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TCNE addition to diacetylene derivatives was examined which carried diphenylamino group at one end. The substituent at the other end is 2-hydroxy-2-propyl group which is considered to bulky group rather than diphenylamino one. The addition proceed at the acetylenic group next to the diphenyl amino group. The result showed steric factor was more important than intramolecular CT interaction.

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