The quantitative excited energy transfer reaction between cationic porphyrins on an anionic clay surface was successfully achieved. The efficiency reached up to ca. 100% owing to the "Size-Matching Rule" as described in the text. It was revealed that the important factors for the efficient energy transfer reaction are (i) suppression of the self-quenching between adjacent dyes, and (ii) suppression of the segregated adsorption structure of two kinds of dyes on the clay surface. By examining many different kinds of porphyrins, we found that tetrakis(1-methylpyridinium-3-yl) porphyrin (m-TMPyP) and tetrakis(1-methylpyridinium-4-yl) porphyrin (p-TMPyP) are the suitable porphyrins to accomplish a quantitative energy transfer reaction. These findings indicate that the clay/porphyrin complexes are promising and prospective candidates to be used for construction of an efficient artificial light-harvesting system.

We have been investigating complexes composed of nanolayered materials with anionic charges such as clay nanosheets and dye molecules such as cationic porphyrins. It was found that the structure of dye assembly on the layered materials can be effectively controlled by the use of electrostatic host-guest interaction. The intermolecular distance, the molecular orientation angle, the segregation/integration behavior, and the immobilization strength of the dyes can be controlled in the clay-dye complexes. The mechanism to control these structural factors has been discussed and was established as a size-matching effect. Unique photochemical reactions such as energy transfer through the use of this methodology have been examined. Almost 100% efficiency of the energy-transfer reaction was achieved in the clay-porphyrin complexes as a typical example for an artificial light-harvesting system. Control of the molecular orientation angle is found to be useful in regulating the energy-transfer efficiency and in preparing photofunctional materials exhibiting solvatochromic behavior. Through our study, clay minerals turned out to serve as protein-like media to control the molecular position, modify the properties of the molecule, and provide a unique environment for chemical reactions.

We present an efficient synthesis of a modified carbon nitride photocatalyst by using supramolecular complexes of cyanuric acid, melamine, and 2,4-diamino-6-phenyl-1,3,5-triazine as precursors. We combined a self-templating approach for morphology control with the modification of photophysical properties by altering the chemical structure of the material. The resulting carbon nitrides exhibit high surface areas, defined morphologies, and a strong enhancement of light absorption in the visible-light region. A detailed analysis shows that the ratio changes of the three raw monomers resulted in different carbon nitride morphologies, absorption, and emission properties, along with the incorporation of different numbers of phenyl groups in the resulting carbon nitride structures. The modified carbon nitrides exhibit superior activity in the photodegradation of rhodamine B, up to 16 times that of bulk carbon nitride. The pyrolysis of rationally chosen supramolecular hydrogen-bonded precursors constitutes a synthetic pathway for the simple one-pot preparation of efficient, metal-free carbon nitride photocatalysts.

This paper proposes a novel methodology to synthesize highly fluorescent gold nanoparticles (NPs) with a maximum quantum yield of 16%, in the near-infrared (IR) region. This work discusses the results of using our (previously developed) matrix sputtering method to introduce mercaptan molecules, α-thioglycerol, inside the vacuum sputtering chamber, during the synthesis of metal NPs. The evaporation of α-thioglycerol inside the chamber enables to coordinate to the "nucleation stage" very small gold nanoclusters in the gas phase, thus retaining their photophysical characteristics. As observed through transmission electron microscopy, the size of the Au NPs obtained with the addition of α-thioglycerol varied from approximately 2-3 nm to approximately 5 nm. Plasmon absorption varied with the size of the resultant nanoparticles. Thus, plasmon absorption was observed at 2.4 eV in the larger NPs. However, it was not observed, and instead a new peak was found at approximately 3.4 eV, in the smaller NPs that resulted from the introduction of α-thioglycerol. The Au NPs stabilized by the α-thioglycerol fluoresced at approximately 1.8 eV, and the maximum wavelength shifted toward the red, in accordance with the size of the NPs. A maximum fluorescent quantum yield of 16% was realized under the optimum conditions, and this value is extremely high compared to values previously reported on gold NPs and clusters (generally ∼1%). To our knowledge, however, Au NPs of size>2 nm usually do not show strong fluorescence. By comparison with results reported in previous literature, it was concluded that these highly fluorescent Au NPs consist of gold-mercaptan complexes. The novel method presented in this paper therefore opens a new door for the effective control of size, photophysical characteristics, and structure of metal NPs. It is hoped that this research contributes significantly to the science in this field.

The mechanism inducing the unique absorption spectral shifts of porphyrin molecules upon adsorption on the clay surface was experimentally confirmed to be the flattening of the meso substituent with respect to the plane of the porphyrin ring. We investigated the spectral shift systematically by using seven types of porphyrin derivatives, differing in their center metal, meso substituent, and number of cationic sites. The aggregation, which usually induces the spectral shift, is suppressed in our clay/porphyrin systems. The adsorption strengths of porphyrin molecules on the clay surface were estimated as the relative adsorption equilibrium constants K rel. The seven types of porphyrins studied had different values of K rel, which can be explained by the steric effect and the Coulomb interaction due to the differences in the molecular structure. The obtained K rel values have interesting information of the photochemical property of the clay/porphyrin complexes. The absorption spectral shifts of the porphyrin Soret bands between those in the bulk solution and those on the clay surface are well related to K rel values. Like this, by the systematic experiments using the series of porphyrin derivatives, it was directly confirmed that the flattening of the molecule is the dominant mechanism for the spectral shift on the surface of inorganic nanosheets.

Saponite-type clays that have different cation exchange capacities were successfully synthesized by hydrothermal synthesis. The structure and properties were analyzed by X-ray diffraction, X-ray fluorescence, (27)Al NMR, FT-IR, thermogravimetric and differential thermal analysis, atomic force microscopy, and cation exchange capacity measurement. The intercharge distances on the synthetic saponite (SS) surfaces were calculated to be 0.8-1.9 nm on the basis of a hexagonal array. The complex formation behavior between SS and cationic porphyrins was examined. It turns out that the average intermolecular distance between porphyrin molecules on the SS surface can be controlled, depending on the charge density of the SS. In the case of tetrakis(1-methylpyridinium-4-yl)porphyrin (H(2)TMPyP(4+)), the average intermolecular distances on the SS surface can be controlled from 2.3 to 3.0 nm on the basis of a hexagonal array. It was also found that absorption maxima of porphyrins depend on the charge density of the SS. The adsorption behavior of porphyrin on the SS surface can be rationally understood by the previously reported "size-matching rule". This methodology using host-guest interaction can realize a unique adsorption structure control of the porphyrin molecule on the SS surface, where the gap distance between guest porphyrin molecules is rather large. These findings will be highly valuable to construct photochemical reaction systems such as energy transfer in the complexes.

Here we report a novel physical approach for thiolate–protected fluorescent gold nanoparticles with a controlled size of the order of a few nanometers. This approach is based on a sputtering of gold into a liquid matrix containing thiolate ligand as a stabilizer at various concentrations, thus no reductant was used. The size of the gold nanoparticles was successfully controlled to range from 1.6 to 7.4 nm by adjusting the thiol concentrations. Surface plasmon absorption was observed in larger nanoparticles, but it was not observed in smaller ones. Such smaller nanoparticles fluoresced at around 670 nm with a small spectral shift according to their size, however, the diameter (1.6–2.7 nm) was very strange to show such red emission compared with photophysical characteristics of reported gold cluster or nanoparticles synthesized by chemical method. By detailed investigations using TEM, HAADF-STEM, XPS, and TGA, and size fractionation by size exclusion chromatography, we finally arrived at the plausible mechanism for the origin of unusual fluorescence property; the obtained gold nanoparticles are not single-crystal and are composed of aggregates of very small components such as multinuclear gold clusters or complexes.

We herein propose a novel methodology to synthesize silver nano-particles with precisely controlled diameters in single nano-meter orders by sputtering into a liquid matrix (polyethylene glycol) containing mercaptans (11-mercaptoundecanoic acid) as an environmental friendly preparation without reductants