Total Synthesis of Icumazole A Using a Modified Cadiot-Chodkiewicz Coupling.

The first total synthesis of myxobacteria metabolite icumazole A (1) is reported. Key steps in the route include an organocatalyzed asymmetric self-aldol reaction followed by an acetate aldol reaction to form the stereotriad present in the oxazole moiety, an intramolecular Diels-Alder reaction to form the isochromanone, and an acetylide addition and selective methylation. The final steps involved a high-yielding modified Cadiot-Chodkiewicz coupling and stereoselective reduction to secure the Z,Z-diene and afford 1.

Bond dissociation energies for Fe2+, Fe2O+, and Fe2O2+ clusters determined through threshold photodissociation in a cryogenic ion trap.

Understanding and controlling the chemical behavior of iron and iron oxide clusters requires accurate thermochemical data, which, because of the complex electronic structure of transition metal clusters, can be difficult to calculate reliably. Here, dissociation energies for Fe2+, Fe2O+, and Fe2O2+ are measured using resonance enhanced photodissociation of clusters contained in a cryogenically cooled ion trap. The photodissociation action spectrum of each species exhibits an abrupt onset for the production of Fe+ photofragments from which bond dissociation energies are deduced for Fe2+ (2.529 ± 0.006 eV), Fe2O+ (3.503 ± 0.006 eV), and Fe2O2+ (4.104 ± 0.006 eV). Using previously measured ionization potentials and electron affinities for Fe and Fe2, bond dissociation energies are determined for Fe2 (0.93 ± 0.01 eV) and Fe2- (1.68 ± 0.01 eV). Measured dissociation energies are used to derive heats of formation ΔfH0(Fe2+) = 1344 ± 2 kJ/mol, ΔfH0(Fe2) = 737 ± 2 kJ/mol, ΔfH0(Fe2-) = 649 ± 2 kJ/mol, ΔfH0(Fe2O+) = 1094 ± 2 kJ/mol, and ΔfH0(Fe2O2+) = 853 ± 21 kJ/mol. The Fe2O2+ ions studied here are determined to have a ring structure based on drift tube ion mobility measurements prior to their confinement in the cryogenic ion trap. The photodissociation measurements significantly improve the accuracy of basic thermochemical data for these small, fundamental iron and iron oxide clusters.

Probing Colossal Carbon Rings.

Carbon aggregates containing between 10 and 30 atoms preferentially arrange themselves as planar rings. To learn more about this exotic allotrope of carbon, electronic spectra are measured for even cyclo[n]carbon radical cations (C14+-C36+) using two-color photodissociation action spectroscopy. To eliminate spectral contributions from other isomers, the target cyclo[n]carbon radical cations are isomer-selected using a drift tube ion mobility spectrometer prior to spectroscopic interrogation. The electronic spectra exhibit sharp transitions spanning the visible and near-infrared spectral regions with the main absorption band shifting progressively to longer wavelength by ≈100 nm for every additional two carbon atoms. This behavior is rationalized with a Hückel theory model describing the energies of the in-plane and out-of-plane π orbitals. Photoexcitation of smaller carbon rings leads preferentially to neutral C3 and C5 loss, whereas rings larger than C24+ tend to also decompose into two smaller rings, which, when possible, have aromatic stability. Generally, the observed charged photofragments correspond to low energy fragment pairs, as predicted by density functional theory calculations (CAM-B3LYP-D3(BJ)/cc-pVDZ). Using action spectroscopy it is confirmed that C14+ and C18+ photofragments from C28+ rings have cyclic structures.

Disentangling Electronic Spectra of Linear and Cyclic Hydrogenated Carbon Cluster Cations, C2n+1H+ (n = 3-10).

Electronic spectra are measured for protonated carbon clusters (C2n+1H+) containing between 7 and 21 carbon atoms. Linear and cyclic C2n+1H+ isomers are separated and selected using a drift tube ion mobility stage before being mass selected and introduced into a cryogenically cooled ion trap. Spectra are measured using a two-color resonance-enhanced photodissociation strategy, monitoring C2n+1+ photofragments (H atom loss channel) as a function of excitation wavelength. The linear C7H+, C9H+, C11H+, C13H+, C15H+, and C17H+ clusters, which are predicted to have polyynic structures, possess sharp 11Σ+ ← X̃1Σ+ transitions with well-resolved vibronic progressions in C-C stretch vibrational modes. The vibronic features are reproduced by spectral simulations based on vibrational frequencies and geometries calculated with time-dependent density functional theory (ωB97X-D/cc-pVDZ level). The cyclic C15H+, C17H+, C19H+, and C21H+ clusters exhibit weak, broad transitions at a shorter wavelength compared to their linear counterparts. Wavelengths for the origin transitions of both linear and cyclic isomers shift linearly with the number of constituent carbon atoms, indicating that in both cases, the clusters possess a common structural motif.

Photo-induced 6π-electrocyclisation and cycloreversion of isolated dithienylethene anions.

The diarylethene chromophore is commonly used in light-triggered molecular switches. The chromophore undergoes reversible 6π-electrocyclisation (ring closing) and cycloreversion (ring opening) reactions upon exposure to UV and visible light, respectively, providing bidirectional photoswitching. Here, we investigate the gas-phase photoisomerisation of meta- (m) and para- (p) substituted dithienylethene carboxylate anions (DTE-) using tandem ion mobility mass spectrometry coupled with laser excitation. The ring-closed forms of p-DTE- and m-DTE- are found to undergo cycloreversion in the gas phase with maximum responses associated with bands in the visible (λmax ≈ 600 nm) and the ultraviolet (λmax ≈ 360 nm). The ring-open p-DTE- isomer undergoes 6π-electrocyclisation in the ultraviolet region at wavelengths shorter than 350 nm, whereas no evidence is found for the corresponding electrocyclisation of ring-open m-DTE-, a situation attributed to the fact that the antiparallel geometry required for electrocyclisation of m-DTE- is energetically disfavoured. This highlights the influence of the carboxylate substitution position on the photochemical properties of DTE molecules. We find no evidence for the formation in the gas phase of the undesirable cyclic byproduct, which causes fatigue of DTE photoswitches in solution.

An ion mobility mass spectrometer coupled with a cryogenic ion trap for recording electronic spectra of charged, isomer-selected clusters.

Infrared and electronic spectra are indispensable for understanding the structural and energetic properties of charged molecules and clusters in the gas phase. However, the presence of isomers can potentially complicate the interpretation of spectra, even if the target molecules or clusters are mass-selected beforehand. Here, we describe an instrument for spectroscopically characterizing charged molecular clusters that have been selected according to both their isomeric form and their mass-to-charge ratio. Cluster ions generated by laser ablation of a solid sample are selected according to their collision cross sections with helium buffer gas using a drift tube ion mobility spectrometer and their mass-to-charge ratio using a quadrupole mass filter. The mobility- and mass-selected target ions are introduced into a cryogenically cooled, three-dimensional quadrupole ion trap where they are thermalized through inelastic collisions with an inert buffer gas (He or He/N2 mixture). Spectra of the molecular ions are obtained by tagging them with inert atoms or molecules (Ne and N2), which are dislodged following resonant excitation of an electronic transition, or by photodissociating the cluster itself following absorption of one or more photons. An electronic spectrum is generated by monitoring the charged photofragment yield as a function of wavelength. The capacity of the instrument is illustrated with the resonance-enhanced photodissociation action spectra of carbon clusters (Cn +) and polyacetylene cations (HC2nH+) that have been selected according to the mass-to-charge ratio and collision cross section with He buffer gas and of mass-selected Au2 + and Au2Ag+ clusters.

Electronic spectra of positively charged carbon clusters-C2n + (n = 6-14).

Electronic spectra are measured for mass-selected C2n +(n = 6-14) clusters over the visible and near-infrared spectral range through resonance enhanced photodissociation of clusters tagged with N2 molecules in a cryogenic ion trap. The carbon cluster cations are generated through laser ablation of a graphite disk and can be selected according to their collision cross section with He buffer gas and their mass prior to being trapped and spectroscopically probed. The data suggest that the C2n +(n = 6-14) clusters have monocyclic structures with bicyclic structures becoming more prevalent for C22 + and larger clusters. The C2n + electronic spectra are dominated by an origin transition that shifts linearly to a longer wavelength with the number of carbon atoms and associated progressions involving excitation of ring deformation vibrational modes. Bands for C12 +, C16 +, C20 +, C24 +, and C28 + are relatively broad, possibly due to rapid non-radiative decay from the excited state, whereas bands for C14 +, C18 +, C22 +, and C26 + are narrower, consistent with slower non-radiative deactivation.

Photoisomerization of Linear and Stacked Isomers of a Charged Styryl Dye: A Tandem Ion Mobility Study.

The photoisomerization behavior of styryl 9M, a common dye used in material sciences, is investigated using tandem ion mobility spectrometry (IMS) coupled with laser spectroscopy. Styryl 9M has two alkene linkages, potentially allowing for four geometric isomers. IMS measurements demonstrate that at least three geometric isomers are generated using electrospray ionization with the most abundant forms assigned to a combination of EE (major) and ZE (minor) geometric isomers, which are difficult to distinguish using IMS as they have similar collision cross sections. Two additional but minor isomers are generated by collisional excitation of the electrosprayed styryl 9M ions and are assigned to the EZ and ZZ geometric isomers, with the latter predicted to have a π-stacked configuration. The isomer assignments are supported through calculations of equilibrium structures, collision cross sections, and statistical isomerization rates. Photoexcitation of selected isomers using an IMS-photo-IMS strategy shows that each geometric isomer photoisomerizes following absorption of near-infrared and visible light, with the EE isomer possessing a S1 ← S0 electronic transition with a band maximum near 680 nm and shorter wavelength S2 ← S0 electronic transition with a band maximum near 430 nm. The study demonstrates the utility of the IMS-photo-IMS strategy for providing fundamental gas-phase photochemical information on molecular systems with multiple isomerizable bonds.

Unimolecular fragmentation and radiative cooling of isolated PAH ions: A quantitative study.

Time-resolved spontaneous and laser-induced unimolecular fragmentation of perylene cations (C20H12 +) has been measured on timescales up to 2 s in a cryogenic electrostatic ion beam storage ring. We elaborate a quantitative model, which includes fragmentation in competition with radiative cooling via both vibrational and electronic (recurrent fluorescence) de-excitation. Excellent agreement with experimental results is found when sequential fragmentation of daughter ions co-stored with the parent perylene ions is included in the model. Based on the comparison of the model to experiment, we constrain the oscillator strength of the D1 → D0 emissive electronic transition in perylene (fRF = 0.055 ± 0.011), as well as the absolute absorption cross section of the D5 ← D0 excitation transition (σabs > 670 Mb). The former transition is responsible for the laser-induced and recurrent fluorescence of perylene, and the latter is the most prominent in the absorption spectrum. The vibrational cooling rate is found to be consistent with the simple harmonic cascade approximation. Quantitative experimental benchmarks of unimolecular processes in polycyclic aromatic hydrocarbon ions like perylene are important for refining astrochemical models.

Photo- and Collision-Induced Isomerization of a Charge-Tagged Norbornadiene-Quadricyclane System.

Molecular photoswitches based on the norbornadiene-quadricylane (NBD-QC) couple have been proposed as key elements of molecular solar thermal energy storage schemes. To characterize the intrinsic properties of such systems, reversible isomerization of a charge-tagged NBD-QC carboxylate couple is investigated in a tandem ion mobility mass spectrometer, using light to induce intramolecular [2 + 2] cycloaddition of NBD carboxylate to form the QC carboxylate and driving the back reaction with molecular collisions. The NBD carboxylate photoisomerization action spectrum recorded by monitoring the QC carboxylate photoisomer extends from 290 to 360 nm with a maximum at 315 nm, and in the longer wavelength region resembles the NBD carboxylate absorption spectrum recorded in solution. Key structural and photochemical properties of the NBD-QC carboxylate system, including the gas-phase absorption spectrum and the energy storage capacity, are determined through computational studies using density functional theory.

Photodetachment and photoreactions of substituted naphthalene anions in a tandem ion mobility spectrometer.

Substituted naphthalene anions (deprotonated 2-naphthol and 6-hydroxy-2-naphthoic acid) are spectroscopically probed in a tandem drift tube ion mobility spectrometer (IMS). Target anions are selected according to their drift speed through nitrogen buffer gas in the first IMS stage before being exposed to a pulse of tunable light that induces either photodissociation or electron photodetachment, which is conveniently monitored by scavenging the detached electrons with trace SF6 in the buffer gas. The photodetachment action spectrum of the 2-naphtholate anion exhibits a band system spanning 380-460 nm with a prominent series of peaks spaced by 440 cm-1, commencing at 458.5 nm, and a set of weaker peaks near the electron detachment threshold corresponding to transitions to dipole-bound states. The two deprotomers of 6-hydroxy-2-naphthoic acid are separated and spectroscopically probed independently. The molecular anion formed from deprotonation of the hydroxy group gives rise to a photodetachment action spectrum similar to that of the 2-naphtholate anion with an onset at 470 nm and a maximum at 420 nm. Near the threshold, the photoreaction with SF6 is observed with displacement of an OH group by an F atom. In contrast, the anion formed from deprotonation of the carboxylic acid group gives rise to a photodissociation action spectrum, recorded on the CO2 loss channel, lying at much shorter wavelengths with an onset at 360 nm and maximum photoresponse at 325 nm.