Supramolecular photochemistry is concerned with systems where non-covalent interactions become significant or dominate in determining the chemistry of guest/host systems. The photocycloaddition of diaryl compounds and the photosensitized oxidation of alkenes included in zeolites, low-density polyethylene films and Nafion membranes is the subject of this report.

Zeolites and microporouos materials continue to attract attention as novel hosts for photochemical reactions. Zeolities are attractive because of their ability to selectivity exchange and incorporate species within the void spaces and interconnecting channels, providing a spatial arrangement of molecules. Our research has primarily focused on intrazeolitic electron transfer from excited Ru(bpy)32+ in supercages of zeolite Y to a series of bipyridinium ions. In the Ru(bpy)32+ viologen-zeolite Y samples, the slowing of the back electron transfer from the bipyridinium radical cation to Ru(bpy)32+ allows for charge propagation via self exchange between diquat molecules. This provides an opportunity for permanent charge separation. When the migrating charge on the diquat radical within the zeolite reaches the surface, it can be transferred to a neutral viologen (PVS) in solution, resulting in permanent charge separation. The advantage of long-lived charge separation can be exploited for useful chemistry if suitable catablysts can be assembled on the zeolities. We have studied Ru(bpy)2 as water oxdiation catalysts. We have demonstrated that synthesis of RuO2 fibers on a zeolite via thermal decomposition of Ru3(CO)12 leads to the most active water decomposition catalyst reported to date. Because of the extensive interest of photochemical water reduction to H2, much is known about catalytic systems usin gone electron catalyst, and even more importantly, that no reaction of viologen occurred with H2 over this catalyst. The present challenge is to incorporate all these elements of the system into an architecture and we are examining zeolite membranes for this purpose.

In this paper, the historicla development of radiationless transitions will be briefly reviewed. The paper will then focus on the ab inition calculations of internal conversion rate constants with emphasis on the case of small polyatomic molecules where the Duschinsky effect is important . As an example, we have chosen the new expressions for singlevibronic level rate constants of radiationless transitions. This type of rate constants is important in femto-second processes.

We present recent results on ablation mechanism, single-pulse laser micropatterning , pulsed-laser deposition(PLD) and particulates formation accompanying laser ablation, with special emplasis on polymers, in particular polymide, (PI), and polytetrafluoroethylene, (PTFE). Ablation of polymers is described on the basis of photothermal bond breaking within the bulk material. Here, we assume a first order chemical reaction, which can be described by an Arrhenius law. Ablation starts when the density of broken bonds at the surface reaches a certain critical value. Single-pulse laser ablation of polyimide shows a clear-length dependence of the threshold fluence. This experimental result strongly supports a thermal ablation model. We discuss the various possibilities and drawbacks of PLD and describe the morphology, physical properties and applications of PTFE films.

Intense excimer laser irradiation of polymer films results in expansion and the following contraction , recovering ithe initial flat surface. The morphological dynamics is meausred directly by nanosecond time-resolved interferometry for polystyrene(PS), polyurethane, and polyimide films. The expansion proceeds with a speed of a few nm/ns , while the contraction depends upon the polymer ; very low contraction for PS, rapid 2 component shrinking for polyurethane, and rapid monotonous decay for polymide. These characteristic behavior are considered from viewpoints of interpenetrating structures of polymers, glass-rubber phase transitioni, thermal diffusion, and photothermal mechanism.

Photoinduced electron transfer of C60 has been studied by the laser photolysis measuring the transient absorption bands in near-IR region. The electron transfer aromatic amines via the triplet state of C60 is confirmed by the decay of the transient absorption bands of the triplet state of C60 and the rise of the anion radical of C60 and the cation radicals of amines. The rate and efficiency of electron transfer are strongly affected by the donor ability of amines and polarity of solvents. Back electron-transfer kinetics is also strongly affected by the solvent polarity.

Dynamics of many ultrafast processes are markedly slowed down in various organized molecular assemblies compared to ordinary liquids. We will show that the solvation dynamics of water molecules is affected amost dramatically and is retarded by 3 ∼4 orders of magnitude in microemulsions, micells and lipids. We will also discuss how the access to fewer water molucules and the drastically altered local pH in an organized asembly affected the excited state proton transfer processes. Finally, we will show how surface second haromonic generation can be used to study the air-water surface.

Microperoxidase 8 (MP8) has been prepared by sequential hydrolysis of cytochrome C by pepsin and trypsin. This five-coordinated heme-octapetide fragment provides a uniques structure to evaluate the electronic coupling efficiency to the iron through axial position and porphyrin edge. At alkali pH, Ru(bpy)2(im)22+ is completely quenched in AcMP8Ru complex . Transient kinetics measurement showed the decay rate to be ~1 $\times$1012S-1. Ruthenium bipyridine complex with a carboxyl group substituted bipyridine has been prepared adn reacted with MR 8 to yield N-terminus bound RuMP8 complex. The luminescence decay rate has been measured as 1 $\times$109S-1. By using semiclassical electron transfer theory, we found the electron transfer efficiency through axial positioin of iron prophyrin is as good through prophyrin edge.

The ratio of dissociation rate $textsc{k}$-acversus the radiative decay rate $textsc{k}$D of the 1O2(1Δg) dimol has been determined to be $1.5\times$109 by its relaxation dynamcis in combination with a two-step O2((1Δg) sensitizing tetratert-butylphthalocoyanine luminescence. Consequently, with a known $textsc{k}$D value of 1.2 $\times$103S-1 , 10$textsc{k}$-ac has been extracted to be 1.8 $\times$1012S-1 CDCl3.

A Spectroscopic study on a pulme produced by a reactive laser pulse irradiates the graphite target in a nitrogen atmosphere, two emission bands of C2(d3IIg longrightarrowa3 IIu, Swan band) and CN(B2$\Sigma$+ longrightarrowX$^2$$\Sigma$+, Violet band ) were observed. By simulation of the optical emissionspectra, spectroscopic temperature of $C_2$ and CN molecules were obtained. The depended of vibrational and rotational temperatures on the laser fluence and distance from the target as well as the pressure dependence of the emission intensities of $C_2$ and CN was examined to elucidate the expansion dynamics of the plume and formation mechanisms of $C_2$and CN molecules.

The use of O-carbamoyloximes as photobase generators was investigated. $\alpha$-Meth-ylbenzilydeneamino phenylcarbamate(2a) and $\alpha$-methyl benzilydeneamino cyclohexylcarbamate(2b) were prepared by the reaction of phenyl or cyclohexyl isocyanates with acetophenone oxime , respectively. Aniline, phenylhydrazine and N, N'-diphenylhydrazine were detected in thephotolysis of 2a and cyclohexylamine and cyclohexylhydrazine in the photolysis of 2b. A monomer having pendant carbamoyloxyimino groups (BGM) was prepared by the reaction fo methancryloyloxyethyl iocyanate with acetophenone oxime, and copolymerized with styrene. The BGM copolymer films turned insoluble on UV irradiation, and the degree of insolubilizationwas increased by post-baking. The photocrosslinking was thought to be due to coupling of resulting pendant aminyl radicals, and the thermal crosslinking was due to association of resulting amino and hydrazino groups by hydrogen bonding. The introduction of epoxy groups into polymer increased the degree of thermal crosslinking by post-baking.

We have introduced the nonresonant holes in the satellite hole spectrum to examine the interaction of two tautomers of thionin to various polynucleotides, including [d(GC)7]2 , [d(AT)7]2 and calf thymus. The saturated depths of nonresonant holes are much reduced upon interacting with [d(GC)7]2 and calf thymus than with [d(AT)7]2 , implying that the binding affinity of thionin to [d(GC)7]2 and calf thymus is stronger than [d(AT)7]2 . In addition, the less perturbation on the exocyclic amino group of the amino -form of thionin upon interacting with [d(AT)7]2 suggests that a direct hydrogen bond formed between the amino group of thionin and the phosphate of nucleic acids is unlikely.