Copper catalyst activation driven by photoinduced electron transfer: a prototype photolatent click catalyst

PET cat. While the copper(II) tren ketoprofenate precatalyst 1 (see picture) is inactive at room temperature in methanol, it is quantitatively and rapidly reduced to its cuprous state upon light irradiation to provide a highly reactive click catalyst. By simply introducing air into the reaction medium the catalysis can be switched off and then switched on again by bubbling argon followed by irradiation.     

Initiation of cationic polymerization by photoinduced electron transfer

The objective of this paper is to discuss: (i) the general approaches to the initiation of cationic polymerization by photinduced electron transfer reactions (ii) the use of photoinduced electron transfer reactions for block copolymer synthesis. For the first, it is concluded that three general methods are currently available which involve reduction of onium salts by (a) photogenerated radicals, (b) photoexcited sensitizers or (c) electron donor compounds in charge transfer complexes. According to this view, a variety of initiating systems are discussed. For the second, recent developments on the application of photoinduced electron transfer reactions to the synthesis of block copolymer of monomers polymerizable with different mechanisms are presented.     

Theory of photoinduced heterogeneous electron transfer

We consider electron injection into the conduction band of a semiconductor, from an electronically excited state of a dye molecule, adsorbed on its surface. For arbitrary width of the conduction band, the survival probability of the excited state can be calculated using a Green's-function approach. We show that the existence of a split-off state can play an important role in the total injection probability. In the wide band limit, the survival probability decays exponentially, but for finite band widths it does not. We further investigate the effect of vibrations on the process. A Green's operator technique may be used to solve this too exactly. We show that the problem may be reduced to a non-Hermitian eigenvalue problem for the vibrational states alone. Exact results can be obtained for arbitrary bandwidth and for a few vibrational degrees of freedom. In the wide band limit, the dynamics is particularly simple and we find that (1) the survival probability of the excited state is unchanged by the inclusion of vibrational motion, but (2) each vibrational state now has a finite lifetime. Numerical results are presented for the effects of reorganization energy, energy of the injecting level, and the variation of the matrix element for the electron injection, on the survival probability of the electron in the excited state. As an illustration of the approach, we also present results of numerical calculation of the absorption spectrum of perylene adsorbed on TiO(2) and compare it with experimental results.     

The radicals formed by photoinduced electron transfer from hypocrellins to electron acceptors

The photoinduced electron transfer from excited singlet and triplet states of hypocrellins to three electron acceptors, namely, methyl viologen chloride (MV), tetrachloro-p-benzoquinone (TCQ) and 2,3-dichloro-5,6-dicyan-p-benzoquinone (DDQ), has been investigated by fluorescence and time-resolved transient absorption spectra. In acetonitrile solution, DDQ and TCQ quenched the fluorescence and T-T absorption of hypocrellins (HA and HB) efficiently, while neither fluorescence nor T-T absorption of them could be quenched by MV. The quenching resulted from the electron transfer between excited hypocrellins and the electron acceptors was controlled by diffusion. The rate constants of electron transfer from excited singlet and triplet of HA to DDQ are 9.20×10¹⁰ dm³ mol^?1 s^?1 and 1.28×10⁹ dm³ mol^?1 s^?1, respectively. The transient absorption spectra of the formed radical cations of hypocrellins are reported.     

Stereoselective fluorescence quenching by photoinduced electron transfer in naphthalene-amine dyads

Intramolecular chiral recognition in electron-transfer-induced fluorescence quenching has been observed for diastereomeric dyads composed of a naphthalene chromophore and an amine.     

Quinone methide generation via photoinduced electron transfer

Photochemical activation of water-soluble 1,8-naphthalimide derivatives (NIs) as alkylating agents has been achieved by irradiation at 310 and 355 nm in aqueous acetonitrile. Reactivity in aqueous and neat acetonitrile has been extensively investigated by laser flash photolysis (LFP) at 355 nm, as well as by steady-state preparative irradiation at 310 nm in the presence of water, amines, thiols, and ethyl vinyl ether. Product distribution analysis revealed fairly efficient benzylation of the amines, hydration reaction, and 2-ethoxychromane generation, in the presence of ethyl vinyl ether, resulting from a [4 + 2] cycloaddition onto a transient quinone methide. Remarkably, we found that the reactivity was dramatically suppressed under the presence of oxygen and radical scavengers, such as thiols, which was usually associated with side product formation. In order to unravel the mechanism responsible for the photoreactivity of these NI-based molecules, a detailed LFP study has been carried out with the aim to characterize the transient species involved. LFP data suggest a photoinduced electron transfer (PET) involving the NI triplet excited state (λ(max) 470 nm) of the NI core and the tethered quinone methide precursor (QMP) generating a radical ions pair NI(?-) (λ(max) 410 nm) and QMP(?+). The latter underwent fast deprotonation to generate a detectable phenoxyl radical (λ(max) 390 and 700 nm), which was efficiently reduced by the radical anion NI(?-), generating detectable QM. The mechanism proposed has been validated through a LFP investigation at 355 nm exploiting an intermolecular reaction between the photo-oxidant N-pentylnaphthalimide (NI-P) and a quaternary ammonium salt of a Mannich base as QMP (2a), in both neat and aqueous acetonitrile. Remarkably, these experiments revealed the generation of the model o-QM (λ(max) 400 nm) as a long living transient mediated by the same reactivity pathway. Negligible QM generation has been observed under the very same conditions by irradiation of the QMP in the absence of the NI. Owing to the NIs redox and recognition properties, these results represent the first step toward new molecular devices capable of both biological target recognition and photoreleasing of QMs as alkylating species, under physiological conditions.     

Life uncertainty broadening in photoinduced electron transfer

Two types of energy-level broadening, one caused by electron exchange between radicals and ground-state molecules, the other by selective sampling at short times, are investigated. Both lead, in accordance with the uncertainty principle, to an increase in the B_1/2 value.     

Magnetic and optical bistability driven by thermally and photoinduced intramolecular electron transfer in a molecular cobalt-iron prussian blue analogue

A soluble molecular analogue of photoresponsive Co/Fe Prussian blues is described within this report. As judged via a variety of spectroscopic, magnetic, and crystallographic methods, electron transfer within the octanuclear complex (below 250 K) converts paramagnetic red crystals into green diamagnetic ones. The color and magnetic changes are associated with the transformation of FeIIILS-CN-CoIIHS units into FeIILS-CN-CoIIILS fragments in manner that is identical to that found for the An[Co(OH2)(6-6m)][Fe(CN)6]m.xH2O (An = alkali metal cation) family of three-dimensional Prussian blues. Moreover, this intramolecular electron transfer can be quantitatively circumvented via rapid thermal quenching and reversed via simple white light irradiation at low temperatures. Remarkably the data suggests that thermally or photoinduced paramagnetic metastable phases are identical and exhibit long relaxation times that approach 10 years at 120 K.     

Salt effects in photoinduced electron transfer reactions

Metal salts and oxygen react synergistically to inhibit back-electron-transfer in photoinduced reactions.     

Creation of superior carboxyfluorescein dyes by blocking donor-excited photoinduced electron transfer

[Structure: see text] Carboxyfluoresceins are widely utilized as fluorescence labeling reagents, but we recently found that their emission intensity is markedly decreased after esterification. On the basis of our hypothesis that the fluorescence decrease is due to a donor-excited photoinduced electron transfer (d-PeT) process, we have developed novel carboxyfluorescein derivatives in which the d-PeT process is hampered, and the emission intensity is not decreased upon esterification. These novel dye derivatives display high quantum yields and are expected to be useful as labeling agents.     

Peculiarities and paradoxes of photoinduced electron transfer reactions

Many chemical reactions involve the electron transfer stage. The kinetics of photoinduced electron transfer reactions is commonly considered in terms of either the transition state theory as preliminary thermally activated reorganization of the medium and reactants (necessary for degeneracy of the electronic levels of the reactants and the products) or nonradiative quantum transitions, which do not require preliminary activation and are observed in the exoergic region. A new approach to the kinetics of such reactions that has been proposed recently considers a substantial reduction of the barrier in the contact reactant pair due to strong electronic interaction and takes into account the intermediate formation of a charge transfer complex. This approach has explained many well-known important features of electron transfer reactions that are inconsistent with the first two theories.     

光敏电子转移异构反应中的盐效应

本文利用四正丁基四氟硼酸铵为探针, 研究了顺式芪和四环烷的9,10-二氰基蒽敏化光异构化的反应机理, 加入四正丁基四氟硼酸铵明显加快顺式芪的异构反应而减慢四环烷的反应。荧光猝灭及激光闪光光解实验证明四正丁基四氟硼酸铵能促进电荷分离过程而生成离子自由基对。从而证实顺式芪的异构化反应是经由离子自由基的历程, 而四环烷则是通过激基复合物机理。     

Low-field CIDNP study of photoinduced electron transfer reactions

Chemically induced dynamic nuclear polarization in low magnetic field (low-field CIDNP) has been detected and studied in photoinduced electron transfer reactions in the polar solvent acetonitrile. For the radical-ion reactions two different approaches to interpret the low-field CIDNP are demonstrated: interpretation of the low-field CIDNP sign on the basis of quality relationships, and numerical calculations of the CIDNP field dependence. Analysis shows that low-field CIDNP in these reactions is sensitive to the value of the electron exchange interactions in radical-ion pairs.     

TTF-porphyrin dyads as novel photoinduced electron transfer systems

A TTF-linked porphyrin dyad and its zinc complex have been synthesized as novel photosystems with a redox-active pendant. The two chromophores of these dyads are not interactive in the absorption spectra, but the fluorescence of the porphyrin chromophore is dramatically quenched by intramolecular electron transfer from the TTF pendant.     

Inverse photoinduced electron transfer in large betaine molecules

We have used ab initio methods to confirm the existence of an inversion in the photoinduced intramolecular electron transfer in large conjugated pyridinium betaines, by examining compounds where an imidazole ring and a pyridinic group are connected by polyenic chains of increasing size. As these intermediary conjugated bridges get longer, an unusual net charge transfer is observed. The conjugated chain becomes a channel for the photoinduced electronic density flow, and the amount of charge at the donor and acceptor groups is reduced, while an inversion in the spatial localization of the frontier orbitals occurs. We discuss the corresponding implications on the nonlinear optical, photochemical and solvatochromic properties of these molecules.     

ESR spectroscopy of the C60 cation produced by photoinduced electron transfer

In this study the existence of the C60 cation produced by photochemically induced electron transfer in the presence of different sensitising molecules is proved for the first time by using ESR spectroscopy. It is demonstrated for triphenylpyryliumtetrafluoroborate (TPP) by this spectroscopic method that the electron transfer from C60 to TPP occurs without an application of a cosensitiser. Furthermore it is shown that the addition of alcohols causes a new radical in the system C60/TPP. The stationary concentration of the C60 cation diminishes even in the presence of a cosensitiser to such a low concentration that it is not detectable by ESR spectrosopy. The spectroscopic study of the sensitiser/C60 system is also extended to the reaction products.     

Carbon-carbon bond cleavage reactions of 1,2-diamines initiated by photoinduced electron transfer

The oxidative photofragmentations of a series of 1,2-diamines have been studied in reaction with photoexcited electron acceptors under a variety of conditions. All the diamines were found to undergo a clean two electron redox reaction (in the presence of trace amounts of water) to produce after cleavage, two free amines, two aldehydes, and the reduced acceptor. Investigation of the role of variables (solvent, acceptor, temperature, isotope effects, etc.) on the quantum yields for diamine fragmentation leads to a mechanistic picture in which the critical step in the reaction is an unassisted fragmentation. Although formally similar to the photoreactions of previously studied aminoalcohols, the photoinduced electron transfer fragmentation reaction of 1,2-diamines shows key mechanistic differences and is apparently both a more general reaction and significantly more rapid in several cases.     

Exciplex intermediates in photoinduced electron transfer of porphyrin-fullerene dyads

The photoinduced electron transfer in differently linked zinc porphyrin-fullerene dyads and their free-base porphyrin analogues was studied in polar and nonpolar solvents with femto- to nanosecond absorption and emission spectroscopies. A new intermediate state, different from the locally excited (LE) chromophores and the complete charge-separated (CCS) state, was observed. It was identified as an exciplex. The exciplex preceded the CCS state in polar benzonitrile and the excited singlet state of fullerene in nonpolar toluene. The behavior of the dyads was modeled by using a common kinetic scheme involving equilibria between the exciplex and LE chromophores. The scheme is suitable for all the studied porphyrin-fullerene compounds. The rates of reaction steps depended on the type of linkage between the moieties. The scheme and Marcus theory were applied to calculate electronic couplings for sequential reactions, and consistent results were obtained.     

Solvent-controlled photoinduced electron transfer between porphyrin and carbon nanotubes

beta-Cyclodextrin (beta-CD)-modified multiwalled carbon nanotubes (MWCNTs) were successfully prepared by reaction of surface-bound carboxylic chloride groups of MWCNTs with aminoethyleneamino-deoxy-beta-CD (ENCD) and comprehensively characterized by FTIR, Raman, and X-ray photoelectron spectroscopy and thermogravimetric and differential thermal analysis. The beta-CD-modified MWCNTs (ENCD-MWCNTs) are highly water-soluble, with a solubility of ca. 9.0 mg x mL(-1). Furthermore, the photoinduced electron transfer (PET) process between tetrakis(4-carboxyphenyl)porphyrin (TCPP) and ENCD-MWCNTs was investigated by means of fluorescence, fluorescence decay, transient absorption spectroscopy, and cyclic voltammetry. Obvious quenching processes were observed upon addition of both MWCNT-COOH and ENCD-MWCNTs to the aqueous solutions of TCPP, indicating that the PET process between TCPP and carbon nanotubes takes place upon irradiation. When 1-adamantane acetic acid was added to the aqueous solutions of TCPP/MWCNT-COOH and TCPP/ENCD-MWCNTs, respectively, the former fluorescence remains, while the latter fluorescence recovers. On the contrary, the fluorescence intensity of TCPP in the DMF solution was hardly decreased upon addition of ENCD-MWCNTs, whereas its fluorescence was quenched in the presence of MWCNT-COOH. The observations indicate that the CD cavities play a vital role on the control of the PET process.