Several inorganic-organic hybrid complexes were synthesized from a synthetic clay (Sumecton SA) and cationic porphyrins (+4 charge). In the clay-porphyrin complexes, the λmax values of the Soret bands of the porphyrins were shifted to longer wavelengths compared to those in water. Two types of complexes were formed depending on the preparation method. One is assigned to a complex in which the porphyrin molecules are adsorbed on the external surfaces of the dispersed clay layers (type b complexes). The other is assigned to a complex in which the porphyrin molecules are intercalated within the stacked clay layers (type c complexes). The aqueous solutions of both types of complexes do not scatter light in the UV-visible wavelength region. Surprisingly, the porphyrin molecules were found to adsorb on the clay sheets as densely packed monolayers with controlled intermolecular gap distance. In type b, the porphyrins are adsorbed as flat monolayers, without discernible aggregation, that precisely neutralize the negative charges of the clay surface. According to fluorescence lifetime measurements, the adsorbed porphyrin molecules have sufficiently long lifetimes to be used as sensitizers. The fluorescence lifetimes of tetrakis (N, N, N-trimethyl-anilinium-4-yl) porphyrin were found to be 4.1 ns in type b complexes and 3.2 ns in type c, while that in water is 9.3 ns. We report here a novel method in which highly dense yet controllable structures without aggregation can be produced as adsorbed layers on clay surfaces for the first time. We propose that the mechanism for this extraordinary monolayer adsorption could be a precise matching of distances between the negatively charged sites on the clay sheets and that between the positively charged sites in the porphyrin molecule. We have termed this the "size-matching effect." * To whom correspondence should be addressed.

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.

The state-of-the-art of research on artificial photosynthesis is briefly reviewed. Insights into how Nature takes electrons from water, the photon-flux density of sunlight, the time scale for the arrival of the next photon (electron-hole) at the oxygen-evolving complex, how Nature solves the photon-flux-density problem, and how we can get through the bottleneck of water oxidation are discussed. An alternate route for a two-electron process induced by one-photon excitation is postulated for getting through the bottleneck of water oxidation.

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.

Photochemical CO2 reduction sensitized by rhenium–bipyridyl complexes has been studied through multiple approaches during the past several decades. However, a key reaction intermediate, the CO2-coordinated Re–bipyridyl complex, which should govern the activity of CO2 reduction in the photocatalytic cycle, has never been detected in a direct way. In this study on photoreduction of CO2 catalyzed by the 4,4′-dimethyl-2,2′-bipyridine (dmbpy) complex, [Re(dmbpy)(CO)3Cl] (1), we successfully detect the solvent-coordinated Re complex [Re(dmbpy)(CO)3DMF] (2) as the light-absorbing species to drive photoreduction of CO2. The key intermediate, the CO2-coordinated Re–bipyridyl complex, [Re(dmbpy)(CO)3(COOH)], is also successfully detected for the first time by means of cold-spray ionization spectrometry (CSI-MS). Mass spectra for a reaction mixture with isotopically labeled 13CO2 provide clear evidence for the incorporation of CO2 into the Re–bipyridyl complex. It is revealed that the starting chloride complex 1 was rapidly transformed into the DMF-coordinated Re complex 2 through the initial cycle of photoreduction of CO2. The observed induction period in the time profile of the CSI-MS signals can well explain the subsequent formation of the CO2-coordinated intermediate from the solvent-coordinated Re–bipyridyl complex. An FTIR study of the reaction mixture in dimethyl sulfoxide clearly shows the appearance of a signal at 1682 cm–1, which shifts to 1647 cm–1 for the 13CO2-labeled counterpart; this is assigned as the CO2-coordinated intermediate, ReII–COOH. Thus, a detailed understanding has now been obtained for the mechanism of the archetypical photochemical CO2 reduction sensitized by a Re–bipyridyl complex.