Electron-transfer photoinduced thermal reactions

The typical results reported in this chapter, clearly demonstrate how the lifetime of excited states and the low-spin/high-spin character of such states can be tuned by pressure. Furthermore, photochemical bond formation and cleavage processes are accelerated or decelerated by pressure, respectively, in a similar way as found for the corresponding thermal reactions. As a result of this, the associative or dissociative nature of such substitution reactions can be characterized. A further characterization of the intimate nature of the reaction mechanism can also be obtained for photochemical isomerization and electron-transfer reactions as reported in Sections V and VI, respectively. The same applies to photoinduced thermal reactions, where the interpretation of the pressure dependence is not complicated by photophysical relaxation processes. The results for the subsequent thermal reactions can be compared with a wealth of information available for such processes [1-6]. Especially the construction of reaction volume profiles has turned out to be a powerful tool in the elucidation of such reaction mechanisms. 

Since the electrostatic potential sharply decreases with increasing distance from the polyelectrolyte cylinder, the degree of reactivity modification by functional groups fixed to the polyion is strongly dependent on the distance from the cylinder surface. Considerable electrostatic potential effects on the photoinduced forward and thermal back electron transfer reactions, which will be discussed in the following chapters, can be attributed to the functional chromophore groups directly attached to the polyelectrolyte back-bone through covalent bonds. 

Although the most numerous investigations of dissociative electron transfer have concerned thermal reactions, photoinduced dissociative electron transfer has also attracted a great deal of recent theoretical and experimental attention. As discussed in Section 6, one of the key questions in the field is whether photoinduced dissociative electron transfers are necessarily endowed with a unity quantum yield as one would predict on purely intuitive grounds. Quantum yield expressions for the concerted and stepwise cases are established and experimental examples are discussed. 

It is a pleasure to acknowledge the essential contribution of Dr. C. P. Andrieux to most of the work reported above as well as that of Dr. D. Lexa in the field of porphyrins, Professor Moiroux and Dr. A. Anne to cation radical reactivity, Dr. M. Robert to photoinduced dissociative electron transfer and to the stepwise/concerted competition and Drs. P. Hapiot and Medebielle to recent work on thermal SRn1 reactions. Many students from our group have also contributed effectively to the work, namely, C. Costentin, G. Delgado, V. Grass, A. Le Gorande, C. Tardy and D. L. Wang. Fruitful and pleasant... 

The thermal Diels-Alder reactions of anthracene with electron-poor olefinic acceptors such as tetracyanoethylene, maleic anhydride, maleimides, etc. have been studied extensively. It is noteworthy that these reactions are often accelerated in the presence of light. Since photoinduced [4 + 2] cycloadditions are symmetry-forbidden according to the Woodward-Hoffman rules, an electron-transfer mechanism has been suggested to reconcile experiment and theory.212 For example, photocycloaddition of anthracene to maleic anhydride and various maleimides occurs in high yield (> 90%) under conditions in which the thermal reaction is completely suppressed (equation 75). 

In contrast to thermal electron-transfer processes, the back-electron transfer (BET) (kbet) in the PET is generally exergonic as well. The apparent contradiction can be resolved by the cyclic process excitation-electron transfer-back-electron transfer in which the excitation energy is consumed. The back-electron transfer is not the formal reverse reaction of the photoinduced-electron-transfer step and so not necessarily endergonic. This has different influences on PET reactions. On the one hand, BET is the reason for energy consumption and low quantum yields. On the other hand, it can cause more complex reaction mechanisms if the... 

Photoinduced intramolecular electron transfer in the donor-acceptor complex 87 (R = H) generates transient charge-separated open-shell species with the remarkably long lifetime of about 75 ps [89]. Dyads that contain Tt-extended tetrathiafulvalene units also form stable cationic species upon oxidation [90]. The dumbbell shaped triad 91 [91-93] (Scheme 4.13) was obtained by carrying out the reaction with the in situ generated bis-diene at room temperature, in the dark and in o-dichlorobenzene as a solvent in 50% yield. The product is thermally unstable and easily undergoes a retro-Diels-Alder reaction [91]. 

Many spectroscopic methods have been employed for the investigation of such systems For example, wide-band, time-resolved, pulsed photoacoustic spectroscopy was employed to study the electron transfer reaction between a triplet magnesium porphyrin and various quinones in polar and nonpolar solvents. Likewise, ultrafast time-resolved anisotropy experiments with [5-(l,4-benzoquinonyl)-10,15,20-triphenylpor-phyrinato]magnesium 16 showed that the photoinduced electron transfer process involving the locally-excited MgP Q state is solvent-independent, while the thermal charge recombination reaction is solvent-dependent . Recently, several examples of quinone-phtha-locyanine systems have also been reported . 

Steady-state photoinduced electrochromism was achieved in organic solutions [34,35], microcrystals [36,37], LB films [7,8,38,39], and polymer films [40- 48] which was due only to the photoinduced electron transfer reaction via the excited state of specific IPCT complexes [49,50], The photochemical coloring and the thermal fading due to the reverse electron transfer were highly reversible in a deaerated atmosphere in all systems [7,8,34 18], The lifetime of colored (blue)... 

The Marcus Inverted Region (MIR) is that part of the function of rate constant versus free energy where a chemical reaction becomes slower as it becomes more exothermic. It has been observed in many thermal electron transfer processes such as neutralization of ion pairs, but not for photoinduced charge separation between neutral molecules. The reasons for this discrepancy have been the object of much controversy in recent years, and the present article gives a critical summary of the theoretical basis of the MIR as well as of the explanations proposed for its absence in photoinduced electron transfer. The role of the solvent receives special attention, notably in view of the possible effects of dielectric saturation in the field of ions. The relationship between the MIR and the theories of radiationless transitions is a topic of current development, although in the Marcus-Hush Model electron transfer is treated as a thermally activated process. 

The Marcus theory is the most widely applied theory used to describe electron transfer reactions and is equally applicable to photoinduced, interfacial and thermally driven electron transfers. The fundamental difference between these processes lies primarily in the nature of the driving force. In the case of heterogeneous electron... 

The fundamental theories behind electron transfer were discussed above in Section 2.1. Indeed, some of the most important empirical proofs for these theories have originated from photoinduced electron transfer in supramolecular donor-acceptor complexes. The difference between thermally and photochemi-cally induced electron transfer lies in both the orbitals participating in the reaction and in the additional thermodynamic driving force provided by the excited state. It is therefore important to consider the redox properties of excited-state species. 

There are three principal modes of ET, namely, thermal, optical and photoinduced ET, and these are shown schematically in Fig. 1. Optical ET differs from photoinduced ET in that ET in the former process results from direct electronic excitation into a charge transfer (CT) or intervalence band, whereas photoinduced ET takes place from an initially prepared locally excited state of either the donor or acceptor groups. Photoinduced ET is an extremely important process and it is widely studied because it provides a mechanism for converting photonic energy into useful electrical potential which may then be exploited in a number of ways. The most famous biological photoinduced ET reaction is, of course, that which drives... 

Aromatic substrates are by far the most commonly used substrates in the rapidly expanding area of photoinduced electron transfer [1,2]. This is obviously due to the favourable location of the frontier molecular orbitals in such compounds. The same factor facilitates the formation of electron transfer donor-acceptor (EDA) complexes both in the ground state (these possibly are intermediates in some thermal reactions, e.g. selected electrophilic substitutions), and in the excited state (exciplexes). 

From these thermal electron transfer reactions, one can expect that the photoinduced electron transfer reaction of the proteins would occur stereoselec-tively, although such a reaction has not been investigated yet. 

Harpoon mechanism Reaction sequence (thermal or photoinduced) between neutral molecular or atomic entities in which long-range electron transfer is followed by a considerable reduction of the distance between donor and acceptor sites as a result of the electrostatic attraction in the ion pair created. 

This review illustrates the above delineated characteristics of electron-transfer activated reactions by analyzing some representative thermal and photoinduced organometallic reactions. Kinetic studies of thermal reactions, time-resolved spectroscopic studies of photoinduced reactions, and free-energy correlations are presented to underscore the unifying role of ion-radical intermediates [29] in—at first glance—unrelated reactions such as additions, insertions, eliminations, redox reactions, etc. (Photoinduced electron-transfer reactions of metal porphyrin and polypyridine complexes are not included here since they are reviewed separately in Chapters 2.2.16 and 2.2.17, respectively.)... 

Photochemical reactions involving photo-excited states can also be catalyzed as well as the thermal reactions of ground states. However, the lifetimes of excited states are usually very short, particularly for the singlet excited states, and accordingly reactions of the excited state should be fast enough to compete with the decay of the excited state to the ground state (typically the lifetime is 10" -10 " s). Hence there seems to be little chance of catalysis to accelerate the reactions of excited states, which are already fast. There are many cases, however, such that photochemical reactions can be accelerated by some added substances which act as catalysts in the photochemical reactions [62-65]. Photoinduced electron transfer reactions can also be accelerated by the presence of an appropriate catalyst [52]. 

This chapter is intended to focus on catalysis in both thermal and photoinduced electron transfer reactions between electron donors and acceptors by investigating the effects of an appropriate substance that can reduce the activation barrier of electron transfer reactions. It is commonly believed that a catalyst affects the rate of reaction but not the point of equilibrium of the reaction. Thus, a substance is said to act as a catalyst in a reaction when it appears in the rate equation but not in the stoichiometric equation. However, autocatalysis involves a product acting as a catalyst. In this chapter, a catalyst is simply defined as a substance which affects the rate of reaction. This is an unambiguous classification, albeit not universally accepted, including a variety of terms such as catalyzed, sensitized, promoted, accelerated, enhanced, stimulated, induced, and assisted. Both thermal and photochemical redox reactions which would otherwise be unlikely to occur are made possible to proceed efficiently by the catalysis in the electron transfer steps. First, factors that accelerate rates of electron transfer are summarized and then each mechanistic viability is described by showing a number of examples of both thermal and photochemical reactions that involve catalyzed electron transfer processes as the rate-determining steps. Catalytic reactions which involve uncatalyzed electron transfer steps are described in other chapters in this section [66-68]. 

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