Tunable light emission from co-assembled structures of benzothiadiazole molecules.

Co-assembled structures possessing tunable light emission from 510-690 nm have been prepared using various compositions of two different 4,7-substituted benzothiadiazole molecules, 1 and 2. The preferential incorporation and co-localization of 1 and 2 to produce co-assemblies are possible because of structural similarities and allow for tuning of morphology and light emission.

Multi-mode waveguides from ultra-long self-assembled hexagonal faceted microtubules of a benzothiadiazole molecule.

Length controlled (µm-mm-cm) self-assembly of hexagonal faceted microtubules has been achieved using a phase-transfer solution processing approach from . The self-assembled structures exhibit both polarized light emission and multi-mode waveguide properties over large length scales. The multi-mode waveguide characteristics are analyzed using a combination of experiment and finite-difference-time-domain calculations.

Expanded π-electron systems, tri(phenanthro)hexaazatriphenylenes and tri(phenanthrolino)hexaazatriphenylenes, that are self-assembled to form one-dimensional aggregates.

This paper reports the self-assembling and electrochemical nature of hexaazatriphenylene-based electron-deficient heteroaromatics with an expanded π-electron system. The tri(phenanthro)hexaazatriphenylenes (TPHAT-Cs) and tri(phenanthrolino)hexaazatriphenylenes (TPHAT-Ns) were prepared by condensation reactions of the corresponding phenanthrenequinones and phenanthrolinediones, respectively, with hexaaminobenzene. Their electron affinity was indicated from cyclic voltammetry measurements, in which the first reduction potentials were evaluated at around -1.7 V (vs Fc/Fc(+)) in dichloromethane. In nonpolar and polar solvents and in the film state, the TPHAT-Cs and TPHAT-Ns formed one-dimensional aggregates with an H-type parallel stacking mode. In the MALDI-TOF mass spectra, significant peaks were seen at several multiples of the parent ion up to tetramer aggregates. The (1)H NMR spectra indicated a line-broadening effect due to the aggregation. The UV-vis and fluorescence spectra showed a concentration dependence, which is attributed to a dynamic exchange between the monomer and aggregate species. The order of the aggregative nature was estimated from the concentration dependence and the fluorescence quantum yield. By replacement of the peripheral aromatic moieties instead of the phenanthrene (TPHAT-Cs) with the phenanthroline (TPHAT-Ns), the aggregative nature was enhanced.

A fluorescence scanning electron microscope.

Fluorescence techniques are widely used in biological research to examine molecular localization, while electron microscopy can provide unique ultrastructural information. To date, correlative images from both fluorescence and electron microscopy have been obtained separately using two different instruments, i.e. a fluorescence microscope (FM) and an electron microscope (EM). In the current study, a scanning electron microscope (SEM) (JEOL JXA8600M) was combined with a fluorescence digital camera microscope unit and this hybrid instrument was named a fluorescence SEM (FL-SEM). In the labeling of FL-SEM samples, both Fluolid, which is an organic EL dye, and Alexa Fluor, were employed. We successfully demonstrated that the FL-SEM is a simple and practical tool for correlative fluorescence and electron microscopy.

Self-assembled fluorescent hexaazatriphenylenes that act as a light-harvesting antenna.

In this paper we report the self-assembling nature of fluorescent hexaazatriphenylenes (HATs) 6a-d with six alkyl/alkoxy-chain-containing biphenyl groups and their application to light-harvesting antennae. In a nonpolar solvent and the film state, the HAT derivatives form one-dimensional aggregates with an H-type parallel stacking mode, which were analyzed by 1H NMR, UV-vis, and steady-state and time-resolved fluorescence spectroscopy. When HAT derivative 7 with six perylenediimide moieties is incorporated into the one-dimensional aggregates, an efficient energy transfer takes place from the self-assembled HAT moiety as a light-harvesting antenna to the perylenediimide moiety as an energy acceptor. Further, when HAT derivative 8 with six triphenylamino moieties is newly added to the light-harvesting system, an intermolecular electron transfer occurs subsequently between the electron-accepting perylenediimide molecule and the electron-donating triphenylamino molecule.

Self-assembling of n-type semiconductor tri(phenanthrolino)hexaazatriphenylenes with a large aromatic core.

[reaction: see text] Large disk-shaped aromatic tri(phenanthrolino)hexaazatriphenylenes 5a, 5b, and 5c with six butyl, dodecyl, and 4-octylphenyl groups, respectively, were self-assembled both in solution and film state to form one-dimensional aggregates. Their n-type semiconducting nature was indicated from CV measurement, in which the first reduction potentials were evaluated at around -1.7 V (vs Fc/Fc(+)) in dichloromethane.

An enantiomeric nanoscale architecture obtained from a pseudoenantiomeric aggregate: covalent fixation of helical chirality formed in self-assembled discotic triazine triamides by chiral amplification.

Covalent fixation of a chiral helical structure which is created in a self-assembling system by a chiral-amplification method based on the sergeants/soldiers principle is reported. Disk-shaped triazine triamides self-assembled to form columnar-type helical aggregates through pi-stacking interactions among the central triphenyltriazine moieties, hydrogen-bonding interactions among the amide groups, and van der Waals interactions among the alkyl groups in nonpolar solvents such as hexane, octane, toluene, and p-xylene. When the achiral triazine triamide soldier component is mixed with a tiny amount of the chiral triazine triamide sergeant component, control of the intrinsic supramolecular helicity of the self-assembled soldier component by the sergeant component leads to chiral amplification and formation of a pseudoenantiomeric aggregate with only one handedness of the helix. The helicity can be preserved by ring-closing olefin metathesis polymerization mediated by Grubbs catalyst when an achiral component with terminal olefinic groups forms the pseudoenantiomeric aggregate in the presence of a tiny amount of the chiral component without olefinic groups. After polymerization and removal of the chiral component, the polymeric architecture obtained from the achiral soldier component is optically active and thus can be regarded as an enantiomeric object in which the chiral information transferred from the chiral sergeant component is preserved. The nanoscale chiral structure is fixed perfectly, as indicated by CD spectroscopic evidence obtained in a polar THF medium at high temperature and low concentration. AFM and TEM observations show a nanoscale fibrous structure with a diameter of 2-4 nm, which corresponds to the molecular size of the triazine triamide monomer.

Novel 2,1,3-benzothiadiazole-based red-fluorescent dyes with enhanced two-photon absorption cross-sections.

This paper reports the two-photon absorbing and orange-red fluorescence emitting properties of a series of new 2,1,3-benzothiadiazole (BTD)-based D-pi-A-pi-D-type and star-burst-type fluorescent dyes. In the D-pi-A-pi-D-type dyes 1-6, a central BTD core was connected with two terminal N,N-disubstituted amino groups via various pi-conjugated spacers. The star-burst-type dyes 8 and 10 have a three-branched structure composed of a central core (benzene core in 8 and triphenylamine core in 10) and three triphenylamine-containing BTD branches. All the BTD-based dyes displayed intense orange-red color fluorescence in a region of 550-689 nm, which was obtained by single-photon excitation with good fluorescent quantum yield up to 0.98 as well as by two-photon excitation. Large two-photon absorption (TPA) cross-sections (110-800 GM) of these BTD dyes were evaluated by open aperture Z-scan technique with a femtosecond Ti/sapphire laser. The TPA cross-sections of D-pi-A-pi-D-type dyes 2-6 with a benzene, thiophene, ethene, ethyne, and styrene moiety, respectively, as an additional pi-conjugated spacer are about 1.5-2.5 times larger than that of 1c with only a benzene spacer. The TPA cross-sections significantly increased in three-branched star-burst-type BTDs 8 (780 GM) with a benzene core and 10 (800 GM) with a triphenylamine core, which are about 3-5 times larger than those of the corresponding one-dimensional sub-units 9 (170 GM) and 11 (230 GM), respectively. The ratios of sigma/e(pi) between three-branched and one-dimensional dyes were 6.5:3.8 (for 8 and 9) and 6.0:4.0 (for 10 and 11), which are larger than those predicted simply on the basis of the chromophore number density (1:1), according to a cooperative enhancement of the two-photon absorbing nature in the three-branched system.

The photochemistry of thiophene S-oxides.

Thiophene S-oxides have been prepared and their photoreactivity has been studied. In many cases, the sulfur moiety of the thiophene S-oxides is deoxygenated. Here, the corresponding thiophenes or hydroxylated thiophenes are isolated. In the case of the photoirradiation of tert-butyl substituted thiophene S-oxides, the oxygen of the sulfoxy unit is incorporated into the heterocyclic ring system and the corresponding furans have been isolated. Also, structures with two thiophene cores have been oxidized to the respective thiophene S-oxides. These molecules undergo photodeoxygenation, a reaction, which is catalysed by (non-oxidized) thiophenes.

Benzothieno and benzofurano annelated estranes.

The preparation of estrone derived benzothieno- and benzofurano fused steroids is described. Keystep is an intramolecular thienyl(/furyl)-ene-yne cyclization of 16-ethynyl-17-heterarylestra-1,3,5(10),16-tetraenes. The cyclization was carried out under Pt as well as under Ru catalysis.

Light-harvesting and energy-transfer system based on self-assembling perylene diimide-appended hexaazatriphenylene.

[reaction: see text]. Six perylene diimide-appended hexaazatriphenylene, HAT-PDI(6), was self-assembled in both solution and film state to form a highly stabilized dimer aggregate, in which an efficient energy transfer occurs from the hexaazatriphenylene core to the perylene-diimide moiety.

Combination of an aromatic core and aromatic side chains which constitutes discotic liquid crystal and organogel supramolecular assemblies.

This paper reports unique and unusual formations of columnar liquid crystals and organogels by self-assembling discotic molecules, which are composed of an aromatic hexaazatriphenylene (HAT) core and six flexible aromatic side chains. In HAT derivatives 3a, with 4'-(N,N-diphenylamino)biphenyl-4-yl chains, 3b, with 4'-[N-(2-naphthyl)-N-phenylamino]biphenyl-4-yl chains, and 3c, with 4'-phenoxybiphenyl-4-yl chains, the two-dimensional hexagonal packings can be created by their self-assembling in the liquid crystalline phase, which were characterized by polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction analysis. In certain solvents, HAT molecules 3a-c can form the viscoelastic fluid organogels, in which one-dimensional aggregates composed of the HAT molecules are self-assembled and entangled into three-dimensional network structures. The organogel structures were analyzed by scanning electron microscopy observation, (1)H NMR, UV-vis, and circular dichroism spectroscopy. In contrast to 3a-c, none of the liquid crystalline and organogel phases could be formed from 3d and 3e with short aromatic side chains including a phenylene spacer, and 3f (except a few specific solutions) and 3g without terminal diarylamino and phenoxy groups. In 3a-c, the aromatic side chains with terminal flexible groups make up soft regions that cooperatively stabilize the liquid crystalline and organogel supramolecular structures together with the hard regions of the hexaazatriphenylene core.

Photoinduced charge separation and charge recombination in the [60]fullerene-diphenylbenzothiadiazole-triphenylamine triad: role of diphenylbenzothiadiazole as bridge.

Photoinduced electron-transfer processes of the newly synthesized [60]fullerene-diphenylbenzothiadiazole-triphenylamine (C60-PBTDP-TPA) triad in polar and nonpolar solvents have been studied by using time-resolved transient absorption and fluorescence measurements from picosecond to microsecond regions. By fluorescence lifetime measurements in picosecond time regions, excitation of the charge-transfer transition of the PBTDP-TPA moiety in C60-PBTDP-TPA induces energy transfer to the C60 moiety generating 1C60*-PBTDP-TPA, competitively with charge separation generating C60*--PBTDP-TPA*+. From 1C60*-PBTDP-TPA, which is generated directly and indirectly, charge separation occurs generating C60*--PBTDP-TPA*+ in polar solvents. The C60*--PBTDP-TPA*+ formed via the singlet excited states decayed within a few nanoseconds as revealed by the picosecond transient absorption spectra. In the nanosecond time region, C60*--PBTDP-TPA*+ is produced slowly, probably via 3C60*-PBTDP-TPA. Lifetimes of such slowly generated C60*--PBTDP-TPA*+ were longer than 1 micros, which are the longest values among the C60-bridge-TPA triad systems reported hitherto at room temperature. Roles of the PBTDP-TPA moiety with twisted intermolecular charge-transfer character playing as energy donor and electron donor in addition to the bridge have been disclosed.

3-Benzyloxy-16-[(N-methyl-N-phenylamino)methylidene]estra-1,3,5(10)-trien-17-one.

In the title compound, C(33)H(35)NO(2), the five-membered ring adopts a half-chair conformation. The N-methyl-N-phenyl-substituted keto-enamine moiety shows a comparatively long Csp(2)-N bond.

Strongly red-fluorescent novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazoles with enhanced two-photon absorption cross-sections.

Novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazole fluorescent dyes connected to the N,N-diarylamino terminus via various type pi-conjugate spacers exhibits large two-photon absorption cross-sections and high fluorescent quantum yields in orange-red color.

2'-Amino-3-methoxypyrimidino[5',4':16,17]estra-1,3,5(10),16-tetraene.

In the title compound, C21H25N3O, the six-membered ring that is fused to two other six-membered rings in the estrane moiety adopts an envelope conformation. The compound shows intermolecular hydrogen bonding of the amine group to an N atom of the pyrimidine moiety, as well as weak intermolecular interactions involving H atoms in the hydrophobic residue of the molecule.

The sonoelectrooxidation of thiophene S-oxides.

Thiophene-S-oxides (thiophene monoxides) are relatively new compounds, less stable than the better-known thiophene-S-dioxides. They are useful as synthons for a range of applications, including in the production of pharmaceuticals. They have interesting photochemical properties, but in this presentation we contrast the electro-oxidative voltammetry of differently substituted derivatives. We also compare carbocyclic compounds such as tetracyclone, the electro-oxidation of which at relatively high potentials has never been reported in silent or insonated conditions.

6-[3-Hydroxy-17-oxoestra-1,3,5(10)-trien-7beta-yl]hexanenitrile.

In the title compound, C(24)H(31)NO(2), ring B adopts a conformation between the boat and twisted-boat forms. This conformation best accommodates adverse intramolecular H.H interactions between the H atoms of the 7beta-substituent and the two nearest ring H atoms. The tilt angle between rings A and D is 28.6 (1) degrees.

Estrano[17,16-e]pyrimidine-peptide conjugates.

The preparation of a steroidal heterocycle linked to the tripeptide Cys-Gly-Cys is described. Initially, an estrane-derived steroidal heterocycle containing an aminopyrimidine ring fused to the 16,17-position of the steroidal nucleus was synthesized. Thereafter, protected amino acids were coupled iteratively by the DCC method, commencing at the amino group of the aminopyrimidine unit.

Triarylation of eta 6-dihydronaphthalene-Cr(CO)3 complexes.

With ease, eta 6-dihydronaphthalene tricarbonylchromium(0) complexes undergo a triple arylation with concomitant ring closure, when submitted to Heck reactions under 'Jeffery conditions'.