Synthesis of Heterocycle-Substituted Bicyclo[3.1.1]heptanes and Aza-bicyclo[3.1.1]heptanes via Photocatalytic Minisci Reaction.

A route toward heterocycle-functionalized bicyclo[3.1.1]heptanes (BCHeps) and aza-bicyclo[3.1.1]heptanes (aza-BCHeps) has been developed, using mild, photocatalytic Minisci-like conditions to introduce various heterocycles at the bridgehead position from readily available N-hydroxyphthalimide esters of the corresponding carboxylic acids. This chemistry enables access to heterocycle-functionalized BCHep-containing structures that are highly relevant in medicinal chemistry research as potential bioisosteres of meta-substituted arenes and pyridines.

Modeling a halogen dance reaction mechanism: A density functional theory study.

Since the discovery of the halogen dance (HD) reaction more than 60 years ago, numerous insights into the mechanism have been unveiled. To date however, the reaction has not been investigated from a theoretical perspective. Density functional theory (DFT) was used to model the potential energy surface linking the starting reagents to the lithiated products for each step in the mechanism using a thiophene substrate. It was found that the lithium-halogen exchange mechanism is critical to understand the HD mechanism in detail and yielded the knowledge that SN 2 transition states (TS) are favored over the four-center type for the lithium-bromine exchange steps. The overall driving force for the HD is thermodynamics, while the kinetic factors tightly control the reaction path through temperature. The SN 2 lithium-bromide TS are barrierless, except the second, which is the limiting step. Finally, the model for the HD is discovered to be a pseudo-clock type, due to a highly favorable bromide catalysis step and the reformation of 2-bromothiophene. © 2016 Wiley Periodicals, Inc.

Photodissociation of ClNO in the 2 1A' state: computational and experimental NO product state distributions.

Ultrafast photodissociation of the 2 (1)A' state of ClNO, which has an absorption spectrum peaking at 335 nm, is studied by computational and experimental methods. New potential-energy surfaces are calculated for the 1 and 2 (1)A' states at the multireference configuration interaction (MRCI) level. Wavepacket dynamics simulations performed both exactly and by using the multiconfiguration time-dependent Hartree method yield essentially identical results. Transition dipole moments at a range of geometries are included in these calculations to correctly model the excitation. Vibrational and rotational state distributions of the NO product are obtained both computationally by analysing the quantum flux on the 2 (1)A' surface and experimentally by use of 3D resonant multiphoton ionisation (REMPI), a variant of the velocity map imaging technique. The nascent NO is found to be only marginally vibrationally excited, with 91% formed in v=0. The calculated NO rotational distribution peaks in the j=45-55 region, which compares favourably to experiment.

The photodissociation of NO(2) by visible and ultraviolet light.

We present velocity map images of the NO, O((3)P(J)) and O((1)S(0)) photofragments from NO(2) excited in the range 7.6 to 9.0 eV. The molecule was initially pumped with a visible photon between 2.82-2.95 eV (440-420 nm), below the first dissociation threshold. A second ultraviolet laser with photon energies between 4.77 and 6.05 eV (260-205 nm) was used to pump high-lying excited states of neutral NO(2) and/or probe neutral photoproducts. Analysis of the kinetic energy release spectra revealed that the NO photofragments were predominantly formed in their ground electronic state with little kinetic energy. The O((3)P(J)) and O((1)S(0)) kinetic energy distributions were also dominated by kinetically 'cold' fragments. We discuss the possible excitation schemes and conclude that the unstable photoexcited states probed in the experiment were Rydberg states coupled to dissociative valence states. We compare our results with recent time-resolved studies using similar excitation and probe photon energies.

Photodissociation of NO2 in the (2) (2)B2 state: the O((1)D2) dissociation channel.

Direct current slice and crush velocity map imaging has been used to probe the photodissociation dynamics of nitrogen dioxide above the second dissociation limit. The paper is a companion to a previous publication [J. Chem. Phys. 128, 164318 (2008)] in which we reported results for the O((3)P(J)) + NO((2)Pi(Omega)) adiabatic product channel. Here we examine the O((1)D(2)) + NO((2)Pi(Omega)) diabatic product channel at similar excitation energies. Using one- and two-color imaging experiments to observe the velocity distributions of state selected NO fragments and O atoms, respectively, we are able to build a detailed picture of the dissociation dynamics. We show that by combining the information obtained from velocity map imaging studies with mass-resolved resonantly enhanced multiphoton ionization spectroscopy it is possible to interpret and fully assign the NO images. By recording two-color images of the O((1)D(2)) photofragments with different polarization combinations of the pump and probe laser fields we also measure the orbital angular momentum alignment in the atomic fragment. We find that the entire O((1)D(2)) photofragment distribution is similarly aligned with most of the population in the M(J) = +/-1 magnetic sublevels. The similarity of the fragment polarizations is interpreted as a signature of all of the O((1)D(2)) atoms being formed via the same avoided crossing. At the photolysis energy of 5.479 52 eV we find that the NO fragments are preferentially formed in v = 1 and that the vibrationally excited fragments exhibit a bimodal rotational distribution. This is in contrast to the unimodal rotational profile of the NO fragments in v = 0. We discuss these observations in terms of the calculated topology of the adiabatic potential energy surfaces and attribute the vibrational inversion and rotational bimodality of the v = 1 fragments to the symmetric stretch and bending motion generated on excitation to the (2) (2)B(2) state.

Photodissociation of NO2 in the (2) (2)B2 state: a slice imaging study and reinterpretation of previous results.

The photodissociation dynamics of nitrogen dioxide have been probed above the second dissociation limit at photolysis wavelengths close to 226 nm. The O((3)P(J))+NO((2)Pi(Omega)) product channel has been examined using direct current slice velocity map imaging of the O((3)P(J)) and NO((2)Pi(Omega)) fragments. Mass-resolved resonantly enhanced multiphoton ionization spectroscopy and velocity map imaging have been used to probe directly the rovibrational population distributions of the NO fragments. We also examine possible interference from the dissociation of N(2)O(4) by investigating the effect of the sample temperature on the O((3)P(J)) fragment energy distributions. The O((3)P(J))+NO((2)Pi(Omega)) dissociation channel has been found to favor the production of vibrationally cold, highly rotationally excited NO((2)Pi(Omega)) products with all three oxygen spin-orbit components. Other minor dissociation channels which produce O((3)P(J)) atoms have also been identified. We discuss the significance of these dissociation channels and present a reinterpretation of previous studies of NO(2) dissociation on excitation to the (2) (2)B(2) state.

Clusters and switchers in globally coupled photochemical oscillators.

We experimentally investigate the transition to synchronization in a population of photochemical oscillators with weak global coupling. Above a critical coupling strength the oscillators join a one-phase group or two-phase clusters. The number of oscillators in each cluster depends on the initial phase distribution, and irregular switching of oscillators between clusters is observed. The fully synchronized state emerges above a second critical coupling strength. In agreement with earlier theory, the experiments demonstrate the importance of population heterogeneity in cluster multistability.

Time-dependent photoionization of azulene: competition between ionization and relaxation in highly excited states.

Pump-probe photoionization has been used to map the relaxation processes taking place from highly vibrationally excited levels of the S(2) state of azulene, populated directly or via internal conversion from the S(4) state. Photoelectron spectra obtained by 1+2(') two-color time-resolved photoelectron imaging are invariant (apart from in intensity) to the pump-probe time delay and to the pump wavelength. This reveals a photoionization process which is driven by an unstable electronic state (e.g., doubly excited state) lying below the ionization potential. This state is postulated to be populated by a probe transition from S(2) and to rapidly relax via an Auger-like process onto highly vibrationally excited Rydberg states. This accounts for the time invariance of the photoelectron spectrum. The intensity of the photoelectron spectrum is proportional to the population in S(2). An exponential energy gap law is used to describe the internal conversion rate from S(2) to S(0). The vibronic coupling strength is found to be larger than 60+/-5 microeV.

Time-resolved photoion and photoelectron imaging of NO(2).

Time-resolved photoion and photoelectron velocity mapped images from NO(2) excited close to its first dissociation limit [to NO(X(2)Pi) + O((3)P(2))] have been recorded in a two colour pump-probe experiment, using the frequency-doubled and frequency-tripled output of a regeneratively amplified titanium-sapphire laser. At least three processes are responsible for the observed transient signals; a negative pump-probe signal (corresponding to a 266 nm pump), a very short-lived transient close to the cross-correlation of the pump and probe pulses but on the 400 nm pump side, and a longer-lived positive pump-probe signal that exhibits a signature of wavepacket motion (oscillations). These transients have two main origins; multiphoton excitation of the Rydberg states of NO(2) by both 266 and 400 nm light, and electronic relaxation in the 1(2)B(2) state of NO(2), which leads to a quasi-dissociated NO(2) high in the 1(2)A(1) electronic ground state and just below the dissociation threshold. The wavepacket motion that we observe is ascribed to states exhibiting free rotation of the O atom about the NO moiety. These states, which are common for loosely bound systems such as a van der Waals complex but unusual for a chemically-bound molecule, have previously been observed in the frequency domain by optical double resonance spectroscopy but never before in the time domain.

Dissociative multiphoton ionization of NO2 studied by time-resolved imaging.

We have studied dissociative multiphoton ionization of NO2 by time-resolved velocity map imaging in a two-color pump-probe experiment using the 400 and 266 nm harmonics of a regeneratively amplified titanium-sapphire laser. We observe that most of the ion signal appears as NO+ with approximately 0.28 eV peak kinetic energy. Approximately 600 fs period oscillations indicative of wave packet motion are also observed in the NO+ decay. We attribute the signal to two competitive mechanisms. The first involving three-photon 400 nm absorption followed by dissociative ionization of the pumped state by a subsequent 266 nm photon. The second involving one-photon 400 nm absorption to the 2B2 state of NO2 followed by two-photon dissociative ionization at 266 nm. This interpretation is derived from the observation that the total NO+ ion signal exhibits biexponential decay, 0.72 exp(-t/90+/-10)+0.28 exp(-t/4000+/-400), where t is the 266 nm delay in femtoseconds. The fast decay of the majority of the NO+ signal suggests a direct dissociation via the bending mode of the pumped state. .

Excited state dynamics and rapid internal conversion in a stable dipole molecule.

The excited singlet state of an azomethine ylide or 'stable dipole' exhibits an ultrafast radiationless relaxation after femtosecond laser excitation. These transients are observed before the excited state decays in an almost activationless manner, the barrier is 440 cm-1, to the ground state with a 1.5 ps lifetime. Cooling of the hot ground state is also apparent in the transient absorption data and in methanol decays with a 5.7 ps lifetime. The viscosity dependence of the fluorescence yield and lifetime in different solvents is small and far less pronounced than in triphenylmethane dyes. Surprisingly, the excited state decay is not due to twisting about the C-N bond of the ylide but it is caused by buckling of one of the rings as the nitrogen atom changes character from sp2 to sp3 hybridisation.