Volume 87, Issue 6

Among various kinds of photochromic compounds, bridged imidazole dimers have been known as fast photo-switch molecules. Bridged imidazole dimers have opened up various potential applications to photochromic lenses and real-time holographic displays. The optical properties of bridged imidazole dimers strongly depend on the bridging moiety to tether two imidazole rings. Therefore, the control of the bridging structure by introducing another photochromic moiety would increase the versatility of bridged imidazole dimers. In this study, we designed and synthesized a new type of the bridged imidazole dimer 1 which has the azobenzene moiety as the photo-responsive linker. The cis – trans isomerization of the azobenzene moiety enables to change the distance between the photogenerated radical pairs. The two structural isomers, cis – 1 and trans – 1 , are observed and both compounds undergo the photochromism to produce the imidazolyl radicals. We found that the two imidazolyl radicals generated from cis – 1 are close enough to form the intramolecular C–N bond, whereas the imidazolyl radicals of trans – 1 undergo the intermolecular recombination reaction due to the long distance between the radicals. Our results demonstrate the control of intra-/intermolecular radical recombination reactions by the combination of the two photochromic compounds.

The advent of ultrafast laser spectroscopy has allowed entirely new possibilities for the investigation of the ultrafast photophysics of inorganic metal-based molecular complexes. In this review we show different regimes where non-Kasha behavior shows up. We also demonstrate that while ultrafast intersystem crossing is a common observation in metal complexes, the ISC rates do not scale with the magnitude of the spin-orbit coupling constant. Structural dynamics and density of states play a crucial role in such ultrafast ISC processes, which are not limited to molecules containing heavy atoms.

The development of multicomponent chemical systems that can perform predetermined functions under external control – i.e., molecular devices – is a challenging task in chemistry and a fascinating objective in the frame of a bottom-up approach to nanostructures. Photochromic units undergo profound changes in their chemical and/or electronic structure upon light excitation, and are highly interesting for the construction of photocontrollable molecular devices, machines and materials. The E–Z photoisomerization of azobenzene – owing to its high efficiency, excellent reversibility and significant physico-chemical differences between the two forms – is a highly useful reaction in this regard. Azobenzene photoisomerization has been known for almost 80 years and has been exploited to implement light-induced functionalities with a large variety of compounds, biomolecules, nanosystems and materials. Here we present some of our recent investigations highlighting how this outstanding photochrome can be utilized to develop (supra)molecular systems with valuable light-induced functionalities.

We have successfully demonstrated plasmon-enhanced photocurrent generation using gold nanoparticle-loaded titanium dioxide single-crystal (TiO 2 ) photoelectrodes with visible-light irradiation. Water molecules serve as an electron source in photocurrent generation, and oxygen evolution occurs due to water oxidation from a gold nanostructured TiO 2 photoelectrode as a half reaction of water splitting. On the basis of this property, the photocurrent generation system was applied to the plasmon-induced water-splitting system using both sides of the same strontium titanate (SrTiO 3 ) single-crystal substrate without an electrochemical apparatus. The chamber on the side of the gold nanoparticles was the anode side, whereas the chamber on the side of the platinum plate was the cathode side. Platinum was used as a co-catalyst for hydrogen evolution. Hydrogen and oxygen were separately evolved from the anode and cathode chambers, respectively. Water splitting was induced with a relatively low chemical bias of 0.23 V due to plasmonic effects based on efficient water oxidation. Similar to the artificial photosynthesis system, we have also demonstrated ammonia formation via nitrogen fixation using ruthenium as a co-catalyst via an analogous setup of the water-splitting system.

This article is an overview of recent work performed in our laboratory on TiO 2 heterogeneous photocatalysis of aqueous systems containing toxic forms of chromium, arsenic, lead, uranium and mercury. The cases of chromium and arsenic are treated in profundity. Photocatalytic treatments can convert the ionic species into their metallic solid form and deposit them over the semiconductor surface, or transform them into less toxic soluble species. When a transformation to the zerovalent state is possible, this allows the recovery of the metal from the waters, with an important economical return. Three types of mechanisms can be considered, all of them taking place through successive thermodynamically allowed monoelectronic electron transfer steps: (a) direct reduction by photogenerated electrons; (b) indirect reduction by intermediates generated by hole or hydroxyl radical oxidation of electron donors (reducing radicals); (c) oxidative removal by holes or hydroxyl radicals. Fundamentals of oxidative or reductive heterogeneous photocatalysis are described, with special emphasis on the role of organic donors present in the medium acting as synergists. This indicates the possibility of simultaneous treatment of pollutants of different chemical structure and properties present in the same medium.

Radicals are easily generated via hydrogen transfer form secondary alcohols or tertiary amines using photochemical sensitization with ketones. They can subsequently add to the electron deficient double bond of furanones. The addition of the alcohols is particularly efficient. Therefore, this reaction was used to characterize and to compare the efficiency of different photochemical continuous flow microreactors. A range of micro-structured reactors were tested and their performances evaluated. The enclosed microchip enabled high space-time-yields but its microscopic dimensions limited its productivity. In contrast, the open microcapillary model showed a greater potential for scale-up and reactor optimization. A 10-microcapillary reactor was therefore constructed and utilized for typical R&D applications. Compared to the corresponding batch processes, the microreactor systems gave faster conversions, improved product qualities and higher yields. Similar reactions have also been carried out with electronically excited furanones and other α,β-unsaturated ketones. In this case, hydrogen is transferred directly to the excited olefin. This reaction part may occur either in one step, i.e., electron and proton are transferred simultaneously, or it may occur in two steps, i.e., the electron is transferred first and the proton follows. In the first case, a C–C bond is formed in the α position of the α,β-unsaturated carbonyl compound and in the second case this bond is formed in the β position. For the first reaction, the influence of stereochemical elements of the substrate on the regioselectivity of the hydrogen abstraction on the side chain has been studied.

By the use of a molecular approach we performed photo-induced water oxidation by combining different photosensitizers and catalysts in order to obtain an efficient system that pave the way to the construction of an artificial photosynthetic system. Different types of molecular catalysts, such as ruthenium and vanadium polyoxometalates or cobalt core stabilized by different organic ligands were combined with ruthenium (II) polypyridine complexes of different nuclearity, mononuclear species like [Ru(bpy) 3 ] 2+ or a tetranuclear dendrimer.

Intense efforts by many research groups for more than 50 years have been directed at biomimetic approaches to understand how enzymes achieve their remarkable rate accelerations. Nevertheless, it was noted in 2003 that, despite numerous efforts to design models for catalyzing the cleavage of such species as phosphate diesters, “none of the several models so far described approaches the enormous catalytic efficiency of natural enzymes”. The same could be said for biomimetics of other enzymes promoting acyl or phosphoryl transfer reactions, particularly those mediated by metal ions such as Zn(II). Clearly other important factors were being overlooked or awaiting discovery. In this manuscript we describe two important effects that we have implemented to accelerate metal ion catayzed phosphoryl and acyl transfer reactions. The first of these relates to a medium effect where the polarity of the solution, as measured by dielectric constant, is reduced from that of water ( ε = 78) to values of 31.5 and 24.3 when the solvent is changed to methanol or ethanol. Among organic solvents these light alcohols are closest to water in terms of structure and properties as well as retaining important H-bonding properties. The second important effect involves a known but difficult to demonstrate mode of catalysis where the leaving group (LG) in a solvolysis reaction is accelerated as it becomes progressively poorer. In the cases described herein, the LG’s propensity to depart from a substrate during the course of reaction is accelerated by coordination to a metal ion in a process known as leaving group assistance, or LGA. These two effects can each impart accelerations of 10 9 –10 17 for certain metal ion catalyzed reactions relative to the corresponding solvent, or base induced reactions.