Investigating the Photodissociation Dynamics of CF2BrCF2I in CCl4 through Femtosecond Time-Resolved Infrared Spectroscopy.

The photodissociation dynamics of CF2BrCF2I in CCl4 at 280 ± 2 K were investigated by probing the C-F stretching mode from 300 fs to 10 µs after excitation at 267 nm using time-resolved infrared spectroscopy. The excitation led to the dissociation of I or Br atoms within 300 fs, producing the CF2BrCF2 or CF2ICF2 radicals, respectively. All nascent CF2ICF2 underwent further dissociation of I, producing CF2CF2 with a time constant of 56 ± 5 ns. All nascent g-CF2BrCF2 isomerized into the more stable a-CF2BrCF2 with a time constant of 47 ± 5 ps. Furthermore, a-CF2BrCF2 underwent a bimolecular reaction with either itself (producing CF2BrCF2Br and CF2CF2) or Br in the CCl4 solution (producing CF2BrCF2Br) at a diffusion-limited rate. The secondary dissociation of Br from a-CF2BrCF2 was significantly slow to compete with the bimolecular reactions. Overall, approximately half of the excited CF2BrCF2I at 267 nm produced CF2BrCF2Br, whereas the other half produced CF2CF2. The excess energies in the nascent radicals were thermalized much faster than the secondary dissociation of I from CF2ICF2 and the observed bimolecular reactions, implying that the secondary reactions proceeded under thermal conditions. This study further demonstrates that structure-sensitive time-resolved infrared spectroscopy can be used to study various reaction dynamics in solution in real time.

Photoacid-induced aqueous acid-base reactions probed by femtosecond infrared spectroscopy.

Acid-base reactions involving an excited photoacid have typically been investigated at high base concentrations, but the mechanisms at low base concentrations require clarification. Herein, the dynamics of acid-base reactions induced by an excited photoacid, pyranine (DA), were investigated in the presence of azide ion (N3-) in D2O solution using femtosecond infrared spectroscopy. Specifically, the spectral characteristics of four species (DA, electronically excited DA (DA*), the conjugate base of DA* (A*-), and the conjugate base of DA (A-)) were probed in the spectral region of 1400-1670 cm-1 in the time range of 1 ps-1 µs. This broad timescale encompassed all the acid-base reactions initiated by photoexcitation at 400 nm; thus, reactions related to both DA* and A- could be probed. Furthermore, changes in the populations of N3- and DN3 were monitored using the absorption bands at 2042 and 2133 cm-1, respectively. Following excitation, approximately half of DA* relaxed to DA with a time constant of 0.44 ± 0.04 ns. The remainder underwent an acid-base reaction to produce A*-, which relaxed to A- with a time constant of 3.9 ± 0.3 ns. The acid-base reaction proceeded via two paths, namely, proton exchange with the added base or simple deuteron release to D2O (protolysis). Notably, all the acid-base reactions were well described by the rate constant at the steady-state limit. Thus, although the acid-base reactions at low base concentrations (< 0.1 M) were diffusion controlled, they could be described using a simple rate equation.

Photoexcitation dynamics of bromodiphenyl ethers in acetonitrile-d3 studied by femtosecond time-resolved infrared spectroscopy.

The efficient decomposition of polybrominated diphenyl ethers (PBDEs), onetime prevalent flame retardants, is central to the reduction of their harmful effects on human health. PBDE photodecomposition is a promising method, but its mechanism and products are not well understood. The photoexcitation dynamics of 3- and 4-bromodiphenyl ethers (BDE-2 and BDE-3) in CD3CN were studied from 0.3 ps to 10 µs using time-resolved infrared spectroscopy. An excitation at 267 nm dissociated the Br atom from BDE-2 and BDE-3 within 0.3 ps and 14 ± 3 ps, respectively, producing a radical compound (R) and a Br atom. About 85% of R formed an intermediate (IM) that weakly interacted with the Br atom and the surrounding CD3CN solvent in 7-12 ps. The remaining R separated from the dissociated Br and underwent slow geminate rebinding (GR) with Br within 35 to 54 ns. The IM competitively engaged in GR with the interacting Br in 40-60 ps or formed CD3CN-bound radical compounds (RS) in 100-130 ps. The RS further degraded via either the dissociation of CD3-producing a cyano-bound diphenyl ether (DE) in 150 or 550 ns-or the deuterium abstraction of CD3CN in 180 or 430 ns-producing a deuterated DE. Overall, 33 ± 3 (22 ± 3)% of the photoexcited BDE-2 (BDE-3) decomposed in CD3CN under 267 nm excitation. Efficient binding of the CD3CN solvent to R deterred the yield-diminishing GR and slowed the rate of product formation. The observed photoexcitation dynamics of BDE suggest methods for the efficient decomposition of PBDE.

meso-Oxoisocorroles: Tunable Antiaromaticity by Metalation and Coordination of Lewis Acids as Well as Aromaticity Reversal in the Triplet Excited State.

The corrole derivative meso-oxoisocorrole has been theoretically predicted to be antiaromatic, despite its formally cross conjugated electronic system. In this study, this prediction has been experimentally proven by the facile preparation of meso-oxoisocorrole via the oxidation of a meso free corrole with MnO2 and its comprehensive characterization using NMR, UV/vis absorption, FT-IR, and transient-absorption spectroscopy, cyclic voltammetry, and X-ray diffraction analysis. Furthermore, the free base meso-oxoisocorrole was metalated by treatment with Ni(acac)2, PdCl2(PhCN)2, and Zn(OAc)2 to give the corresponding metal complexes. These complexes are more strongly antiaromatic, and their degree of paratropicity depends on their planarity. Thus, fine tuning of their antiaromaticity was achieved with concomitant modulation of their HOMO-LUMO gaps. In the presence of tris(pentafluorophenyl)borane, their antiaromaticity is significantly enhanced due to the elongation of the C═O bond, which promotes the polarized C+-O- resonance state. Furthermore, a distinct frequency shift of the C═O vibrational mode in the triplet state was observed in the time-resolved IR spectra in accordance with the Baird rule, which indicates aromaticity reversal in the excited state.

Complete photodissociation dynamics of CF2I2 in solution.

Photodissociation dynamics of CF2I2 in cyclohexane were evaluated by probing the C-F stretching mode over a wide time range after ultraviolet excitation using femtosecond infrared spectroscopy. After the ultrafast (<0.2 ps) state-selective photodissociation of CF2I2 as in the gas phase (267 nm excitation led to exclusive three-body dissociation (CF2 + I + I), 350 nm to exclusive two-body dissociation (CF2I + I), and 310 nm to a mixture of three- and two-body dissociations), various secondary reactions were observed. Once produced, some nascent CF2 radicals immediately formed a complex with the departing I atom (ICF2), which produced either CF2I or CF2 radicals. The produced CF2I geminately recombined with the I atom, whereas the CF2 radical reacted bimolecularly to produce C2F4 with a diffusion-limited rate constant of 8.1 × 109 M-1 s-1. Some nascent CF2I radicals were produced with sufficient excess energy to further dissociate into CF2 and I, or immediately reacted with the dissociated I atom to form the I2-CF2 isomer that rapidly dissociated into CF2 and I2. Other nascent CF2I radicals geminately recombined with the I atom with various time constants. Thus, the nascent photoproducts, CF2 and CF2I take various reaction paths: complex formation, secondary dissociation, isomer formation, and fast and slow germinate rebindings. The ensuing reaction path of the nascent photoproduct is dictated by its internal energy as well as solvent environment, which leads to different interactions between the photoproduct and solvent. Measurement over a broad time range with a structure-sensitive probe could reveal the fate of all the reaction intermediates, which allows evaluation of the complete reaction dynamics in solution.

Rotational Isomerization of Carbon-Carbon Single Bonds in Ethyl Radical Derivatives in a Room-Temperature Solution.

The rotational isomerization of 1,2-disubstituted ethyl radical derivatives, reaction intermediates often found in the reaction of 1,2-disubstituted ethane derivatives, has never been measured because of their short lifetime and ultrafast rotation. However, the rotational time constant is critical for understanding the detailed reaction mechanism involving these radicals, which determine the stereoisomers of compounds produced via the intermediates. Using time-resolved infrared spectroscopy, we found that the CF2BrCF2 radical in a CCl4 solution rotationally isomerizes with a time constant of 47 ± 5 ps at 280 ± 2 K. From this value and the rotational barrier heights of related compounds, CH3CH2 and CH3CH2CHCH3 radicals in CCl4 were estimated to rotationally isomerize within 1 ps at 298 K, considerably faster than ethane and n-butane, which rotationally isomerize with time constants of 1.8 and 81 ps, respectively. The time constant for the rotational isomerization was similar to that calculated using transition state theory with a transmission coefficient of 0.75.

Conformer-Specific Photodissociation Dynamics of CF2ICF2I in Solution Probed by Time-Resolved Infrared Spectroscopy.

The photodissociation dynamics of CF2ICF2I in solution was investigated from 0.3 ps to 100 µs, after the excitation of CF2ICF2I with a femtosecond UV pulse. Upon excitation, one I atom is eliminated within 0.3 ps, producing a haloethyl radical having a classical structure: anti-CF2ICF2 and gauche-CF2ICF2. All the nascent gauche-CF2ICF2 radicals reacted with the dissociated I atom within the solvent cage to produce a complex, I2··C2F4, in <1 ps. The quasi-stable I2··C2F4 complex in CCl4 (CH3CN or CD3OH) further dissociated into I2 and C2F4 with a time constant of 180 ± 5 (46 ± 3) ps. Some of the anti-CF2ICF2 radicals also formed the I2··C2F4 complex with a time constant of 1.5 ± 0.3 ps, while the remaining radicals underwent secondary elimination of I atom in a few nanoseconds. The time constant for the secondary dissociation of I atom from the anti-CF2ICF2 radical was independent of the excitation wavelength, indicating that the excess energy in the nascent radical is relaxed and that the secondary dissociation proceeds thermally. The formation of the I2··C2F4 complex and the thermal dissociation of the anti-CF2ICF2 radical clearly demonstrate that even a weakly interacting solvent plays a significant role in the modification and creation of reaction.