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We report the first successful use of consecutive two-photon accumulation of visible light energy to obtain ultra-high oxidation potentials (> +3 V vs. saturated calomel electrode) enabled by a new class of rationally designed cyclic triarylamine photocatalysts. We demonstrate its practical and synthetic utility in a series of reactions of electron deficient arenes and fluoroarenes with N-nucleophiles. We identified that the photocatalytic reaction is initiated by the lowest excited state of the photocatalyst’s radical cation which abstracts an electron from the substrate only at non-diffusive/direct contact encounters, i.e. the omnipresence of substrate as co-solvent, since the excited radical cation lives only for ps. Neither pre-assembly nor a specific ‘anti-Kasha’ reactivity of a higher excited electronic state is observed. This method may serve as a promising basis for yet unexplored chemical reactions of substrates with very high oxidation potential and presents an attractive alternative to existing methods.

Transition metal complexes capable of releasing small-molecule messengers such as carbon monoxide and nitric oxide upon photoactivation are versatile tools in various fields of chemistry and biology. In this work, we report on the ultrafast photochemistry of [Mo(CO)2(NO)(iPr3tacn)]PF6 (iPr3tacn = 1,4,7-triisopropyl-1,4,7-triazacyclononane), which was synthesized and subsequently characterized in continuous illumination studies and with femtosecond UV-pump/UV-probe and UV-pump/MIR-probe spectroscopy, as well as with stationary calculations. The experimental and theoretical results demonstrate that while the photodissociation of one of the two CO ligands upon UV excitation can be inferred both on an ultrafast timescale as well as under exposure times of several minutes, no evidence of NO release is observed under the same conditions. The binding mode of the diatomic ligands is impacted by the electronic excitation, and excited molecules are observed on a timescale of tens of picoseconds before CO is released from the coordination sphere. Furthermore, based on calculated potential energy scans, we suggest that photolysis of NO could be possible after a subsequent excitation of an electronically excited state with a second laser pulse, or by accessing low-lying excited states that otherwise cannot be directly excited by light.

Excitation with shaped femtosecond laser pulses is a logical extension of coherent two-dimensional (2D) spectroscopy. Here we combine quantum control and information from 2D spectroscopy to analyze the initial steps in three competing reaction pathways of an isomerizing merocyanine dye. Besides the achievement of control objectives, we show how excitation with tailored pulses can be used to retrieve photochemical information that is inaccessible or experimentally demanding to obtain with other approaches.

In photoinduced molecular reaction dynamics, the effects of electronic charge redistribution can lead to multiple pathways that are determined by the nature of the initial structures involved and the environment the molecule of interest is studied in. The β-diketones are a common example of this complexity. They show keto-enol tautomerism that is almost totally shifted toward the enolic form. However, compared to the gas phase, the photochemistry proceeds completely differently by virtue of the solvent environment for these compounds, which are used in commercial sunscreen agents due to a high absorption in the ultraviolet (UV) and fast deactivation processes. We disclose these dynamics by investigating three symmetrical β-diketones in various solvents. To observe these effects on an ultrafast time scale directly in the UV spectral region where the relevant electronic transitions take place, we have developed and employed femtosecond transient absorption with detection capability in the deep UV. Our studies confirm that electronic excitation of the chelated enol form does not lead to any ultrafast photochemistry other than proton transfer followed by rotamerization. The formation of the nonchelated conformers takes place on a picosecond time scale through a dark state, whereas the recovery to the stable chelated enol form is a comparably slow process.

Ultraviolet irradiation of a manganese-tricarbonyl CO-releasing molecule (CORM) in water eventually leads to the liberation of some of the carbon monoxide ligands. By ultraviolet pump/mid-infrared probe femtosecond transient absorption spectroscopy in combination with quantum chemical calculations, we could disclose for the exemplary compound [Mn(CO)3(tpm)](+) (tpm = tris(2-pyrazolyl)methane) that only one of the three carbonyl ligands is photochemically dissociated on an ultrafast time scale and that some molecules may undergo geminate recombination.

We report the photochemistry of two ring-open isomers, namely TTC and TTT, of a bidirectional photoswitchable spiropyran, 6,8-dinitro-1',3',3'-trimethylspiro[2H-1-benzopyran-2,2'-indoline] (6,8-dinitro BIPS). Both isomers are capable of ring closure after excitation with visible fs laser pulses, as disclosed by pump-wavelength-dependent transient absorption experiments in the visible spectral range. The main isomer TTC has its maximum absorption at 560 nm, whereas the minor isomer TTT is red-shifted (600 nm). The excited-state lifetimes differ strongly (τ ≈ 900 ps for TTT and τ ≈ 95 ps for TTC), nevertheless the quantum efficiencies for ring closure (40% for TTC and 35% for TTT) and isomerization (1-2% for TTC and 1-2% for TTT) are comparable. With regard to the bidirectional photoswitching capabilities, 6,8-dinitro BIPS is the first molecular switch based on a 6π-electrocyclic reaction where both ring-open isomers are capable of ring closure.

We report on bidirectional photochemical switching of 6,8-dinitro-1',3',3'-trimethylspiro[2H-1-benzopyran-2,2'-indoline] (6,8-dinitro-BIPS) between the ring-closed spiropyran and the ring-open merocyanine form. This is studied by femtosecond three-color pump-repump-probe experiments. Both ring opening and ring closure are photoinduced. Completion of an entire cycle, consisting of opening and subsequent closure, can be achieved within 40 ps. A much shorter time (

We disclose the light-induced dynamics and ultrafast formation of several photoproducts from the manifold of reaction pathways in the photochemistry of 5-diazo Meldrum's acid (DMA), a photoactive compound used in lithography, by femtosecond mid-infrared transient absorption spectroscopy covering several nanoseconds. After excitation of DMA dissolved in methanol to the second excited state S(2), 70% of excited molecules relax back to the S(0) ground state. In competing processes, they can undergo an intramolecular Wolff rearrangement to form ketene, which reacts with a solvent molecule to an enol intermediate and further to carboxylate ester, or they first relax to the DMA S(1) state, from where they can isomerize to a diazirine and via an intersystem crossing to a triplet carbene. For a reliable identification of the involved compounds, density functional theory calculations on the normal modes and Fourier transform infrared spectroscopy of the reactant and the photoproducts in the chemical equilibrium accompany the analysis of the transient spectra. Additional experiments in ethanol and 2-propanol lead to slight spectral shifts as well as elongated time constants due to steric hindrance in transient spectra connected with the ester formation channel, further substantiating the assignment of the occurring reaction pathways and photoproducts.

International audience; At the microscopic level, multidimensional response functions, such as the nonlinear optical susceptibility or the time-ordered response function, are commonly used tools in nonlinear optical spectroscopy for determining the nonlinear polarization resulting from an arbitrary excitation. In this Account, we point out that the approach successfully developed for the nonlinear polarization can also be used in the case of a directly observable macroscopic quantity. This observable can be, for example, the electric field radiated in a nonlinear mixing experiment, the rate of fluorescence resulting from one- or two-photon absorption, or the rate of a photochemical reaction. For each of these physical processes, perturbation theory can be used to expand the measured quantity in a power series of the exciting field, and an appropriate global response function can be introduced for each order of perturbation. At order n, the multidimensional response function will depend on n variables (either time or frequency) and have the same general properties as the nonlinear susceptibility resulting, for example, from time invariance or causality. The global response function is introduced in this Account in close analogy with the nonlinear susceptibility or the time-ordered microscopic response. We discuss various applications of the global response function formalism. For example, it can be shown that in the weak field limit, a stationary signal induced in a time-invariant system is independent of the spectral phase of the exciting field. Although this result had been demonstrated previously, the global response function enables its derivation in a more general way because no specific microscopic model is needed. Multidimensional spectroscopy is obviously ideally suited to measure the global multidimensional response function. It is shown that the second (or third)-order response can be exactly measured with 2D (or 3D) spectroscopy by taking into account the exact shape of the exciting pulses. In the case of a 2D measurement of the third-order response, a particular projection of the complete 3D response function is actually measured. This projection can be related to a mixed time and frequency representation of the response function when the pulses are assumed to be infinitely short. We thus show that the global response function is a useful tool for deriving general results and that it should help in designing future experimental schemes for femtosecond spectroscopy. Cop. 2009 American Chemical Society.