Metastable Isomers Research Articles

Transient isomers in the photodissociation of bromoiodomethane

The photochemistry of halomethanes is fascinating for the complex cascade reactions toward either the parent or newly synthesized molecules. Here, we address the structural rearrangement of photodissociated CH2IBr in methanol and cyclohexane, probed by time-resolved X-ray scattering in liquid solution. Upon selective laser cleavage of the C-I bond, we follow the reaction cascade of the two geminate geometrical isomers, CH2I-Br and CH2Br-I. Both meta-stable isomers decay on different time scales, mediated by solvent interaction, toward the original parent molecule. We observe the internal rearrangement of CH2Br-I to CH2I-Br in cyclohexane by extending the time window up to 3 μs. We track the photoproduct kinetics of CH2Br-I in methanol solution where only one isomer is observed. The effect of the polarity of solvent on the geminate recombination pathways is discussed.

Detection of interstellar HCS and its metastable isomer HSC: new pieces in the puzzle of sulfur chemistry.

We present the first identification in interstellar space of the thioformyl radical (HCS) and its metastable isomer HSC. These species were detected toward the molecular cloud L483 thanks to observations carried out with the IRAM 30m telescope in the λ 3 mm band. We derive beam-averaged column densities of 7 × 1012 cm-2 for HCS and 1.8 × 1011 cm-2 for HSC, which translate to fractional abundances relative to H2 of 2 × 10-10 and 6 × 10-12, respectively. Although the amount of sulfur locked by these radicals is low, their detection allows to put interesting constraints on the chemistry of sulfur in dark clouds. Interestingly, the H2CS/HCS abundance ratio is found to be quite low, ~ 1, in contrast with the oxygen analogue case, in which the H2CO/HCO abundance ratio is around 10 in dark clouds. Moreover, the radical HCS is found to be more abundant than its oxygen analogue, HCO. The metastable species HOC, the oxygen analogue of HSC, has not been yet observed in space. These observational constraints are confronted with the outcome of a recent model of the chemistry of sulfur in dark clouds. The model underestimates the fractional abundance of HCS by at least one order of magnitude, overestimates the H2CS/HCS abundance ratio, and does not provide an abundance prediction for the metastable isomer HSC. These observations should prompt a revision of the chemistry of sulfur in interstellar clouds.

Photoswitching an Isolated Donor-Acceptor Stenhouse Adduct.

Donor-acceptor Stenhouse adducts (DASAs) are a new class of photoswitching molecules with excellent fatigue resistance and synthetic tunability. Here, tandem ion mobility mass spectrometry coupled with laser excitation is used to characterize the photocyclization reaction of isolated, charge-tagged DASA molecules over the 450-580 nm range. The experimental maximum response at 530 nm agrees with multireference perturbation theory calculations for the S1 ← S0 transition maximum at 533 nm. Photocyclization in the gas phase involves absorption of at least two photons; the first photon induces Z-E isomerization from the linear isomer to metastable intermediate isomers, while the second photon drives another E-Z isomerization and 4π-electrocyclization reaction. Cyclization is thermally reversible in the gas phase with collisional excitation.

Heteroaryl-linked norbornadiene dimers with redshifted absorptions.

Development of Molecular Solar Thermal (MOST) systems for harvesting and storing solar energy is based on molecular photoswitches that undergo photoisomerizations to metastable isomers. One challenge is to achieve low-molecular weight molecules that absorb at sufficiently long wavelengths to match the solar spectrum. Here we show that this can be achieved by linking two norbornadiene (NBD) photoswitches to a central heterocycle, thiophene or carbazole, via alkyne appendages. In this approach, the same heteroaryl is used to tune the properties of two photoswitches at the same time, thereby keeping the molecular weight as low as possible. A series of NBD dimers was prepared by Sonogashira coupling reactions, and these compounds showed remarkable redshifted absorptions, with onsets of absorption as high as 468 nm, and thermal half-lives ranging from 44 seconds to 16 hours.

Theoretical study of substituent and charge effects on the thermal cis → trans isomerization of ortho-fluoroazobenzenes photoswitches

Besides the photochromism isomerization, scientists are likely to focus more and more on the influence on the electrochemical reduction conditions of the azobenzene isomerization process. Diverse azobenzene compounds were chosen to study the behavior of their trans and cis isomers upon electrochemical reduction. Hence, thermal reaction mechanisms for the neutral, cationic and anionic azobenzene derivatives isomerization with a wide variety of electron-donating and electron-withdrawing groups in the para-position of the benzene ring in ground state have been systematically examined applying the density functional theory method. Some prominent changes in structure, energy barrier and reaction rate arose from charge changes of azobenzenes have been detected and interpreted in terms of the strengths of substituents, the polarity of solvents and charge effect. Our findings indicate that the radical anion of the cis isomer can isomerize to the corresponding trans configured counterpart rapidly with a tremendously enhanced rate and obvious decreased energy barriers with respect to the neutral species as the distribution of the electron density changed, signifying that the metastable isomer of a photoswitch is able to isomerize to the more stable one catalytically upon reduction and the charge effect has obvious influence on the reaction mechanism.

ComprehensiveAm242mneutron-induced reaction cross sections and resonance parameters

The $^{242}\mathrm{Am}$ metastable isomer's neutron-induced destruction mechanisms were studied at the Los Alamos Neutron Science Center using the Detector for Advanced Neutron-Capture Experiments array with a compact parallel-plate avalanche counter. New $^{242\mathrm{m}}\mathrm{Am}$ neutron-capture cross sections were determined from 100 meV to 10 keV, and the absolute scale was set with respect to a concurrent measurement of the well-known $^{242\mathrm{m}}\mathrm{Am}$ neutron-induced-fission cross section. The new fission cross section spans an energy range from 100 meV to 1 MeV and was normalized to the ENDF/B-VII.1 evaluated cross section to set the absolute scale. Our $^{242\mathrm{m}}\mathrm{Am}(n,f)$ cross section agrees well with the cross section of Browne et al. [Phys. Rev. C 29, 2188 (1984)] over this large energy interval. The new neutron-capture cross section measurement complements and agrees well with our recent results reported below 1 eV in Buckner et al. [Phys. Rev. C 95, 024610 (2017)]. This new work comprises the most comprehensive study of $^{242\mathrm{m}}\mathrm{Am}(n,\ensuremath{\gamma})$ above thermal energy. Neutron-induced resonance energies and parameters were deduced with the sammy $R$-matrix code for incident neutron energies up to 45 eV, and the new average ${\mathrm{\ensuremath{\Gamma}}}_{\ensuremath{\gamma}}$ is $13%$ higher than the evaluated average $\ensuremath{\gamma}$ width.

Direct Observation of the Ultrafast Evolution of Open-Shell Biradical in Photochromic Radical Dimer.

Delocalized biradicals have been extensively studied because of fundamental interests to singlet biradicals and several potential applications such as to two-photon absorption materials. However, many of the biradical studies only focus on the static properties of the rigid molecular structures. It is expected that the biradical properties of the delocalized biradicals are sensitive to the subtle changes of the molecular structures and their local environments. Therefore, the studies of the dynamic properties of the system will give further insight into stable radical chemistry. In this study, we directly probe the ultrafast dynamics of the delocalized biradical of a photochromic radical dimer, pentaarylbiimidazole (PABI), by time-resolved visible and infrared spectroscopies and quantum chemical calculations with the extended multistate complete active space second-order perturbation theory (XMS-CASPT2). While the photogenerated transient species was considered to be a single species of the biradical, the present ultrafast spectroscopic study revealed the existence of two transient isomers differing in the contributions of biradical character. The origin of the two metastable isomers is most probably due to the substantial van der Waals interaction between the phenyl rings substituted at the imidazole rings. Unraveling the temporal evolution of the biradical contribution will stimulate to explore novel delocalized biradicals and to develop biradical-based photofunctional materials utilizing the dynamic properties.

Halogen bonding stabilizes a cis-azobenzene derivative in the solid state: a crystallographic study.

Crystals of trans- and cis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastable cis-isomer, allowing single crystals of the cis-azobenzene to be grown. Structural analysis on the cis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of the cis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both the trans- and cis-isomers. Due to the rarity of cis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding.

Cross-sections of residual nuclei from deuteron irradiation of thin thorium target at energy 7 GeV

The residual nuclei yields are of great importance for the estimation of basic radiation-technology characteristics (like a total target activity, production of long-lived nuclides etc.) of accelerator driven systems planned for transmutation of spent nuclear fuel and for a design of radioisotopes production facilities. Experimental data are also essential for validation of nuclear codes describing various stages of a spallation reaction. Therefore, the main aim of this work is to add new experimental data in energy region of relativistic deuterons, as similar data are missing in nuclear databases. The sample made of thin natural thorium foil was irradiated at JINR Nuclotron accelerator with a deuteron beam of the total kinetic energy 7 GeV. Integral number of deuterons was determined with the use of aluminum activation detectors. Products of deuteron induced spallation reaction were qualified and quantified by means of gamma-ray spectroscopy method. Several important spectroscopic corrections were applied to obtain results of high accuracy. Experimental cumulative and independent cross-sections were determined for more than 80 isotopes including meta-stable isomers. The total uncertainty of results rarely exceeded 9%. Experimental results were compared with MCNP6.1 Monte-Carlo code predictions. Generally, experimental and calculated cross-sections are in a reasonably good agreement, with the exception of a few light isotopes in a fragmentation region, where the calculations are highly under-estimated. Measured data will be useful for future development of high-energy nuclear codes. After completion, final data will be added into the EXFOR database.

A DFT Study of Multimode Switching in a Combined DHA/VHF-DTE/DHB System for Use in Solar Heat Batteries

Development of photochromic molecules for solar energy storage has two major challenges: (i) to store a sufficient amount of energy in the metastable isomer and (ii) to control the energy-releasing step, i.e., setting it on hold until the energy is needed. Combining the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch with the dithienylethene/dihydrothienobenzothiophene (DTE/DHB) photoswitch could potentially meet these challenges. The combined multimode switch is studied by density functional theory in order to predict its energy storage properties and spectral behavior in various solvents before discussing its suitability for use in solar heat batteries. An energy storage capacity of 0.17 MJ/kg is calculated which corresponds to a specific energy of 46 Wh/kg—slightly larger than that of a common lead–acid car battery (∼40 Wh/kg) but still only one-fourth of lithium-ion batteries (100–250 Wh/kg). The usual trend for 1,8a-dihydroazulene-1,1-dicarbonitrile and its derivatives is for their ene...

Electrocatalytic Z → E Isomerization of Azobenzenes.

A variety of azobenzenes were synthesized to study the behavior of their E and Z isomers upon electrochemical reduction. Our results show that the radical anion of the Z isomer is able to rapidly isomerize to the corresponding E configured counterpart with a dramatically enhanced rate as compared to the neutral species. Due to a subsequent electron transfer from the formed E radical anion to the neutral Z starting material the overall transformation is catalytic in electrons; i.e., a substoichiometric amount of reduced species can isomerize the entire mixture. This pathway greatly increases the efficiency of (photo)switching while also allowing one to reach photostationary state compositions that are not restricted to the spectral separation of the individual azobenzene isomers and their quantum yields. In addition, activating this radical isomerization pathway with photoelectron transfer agents allows us to override the intrinsic properties of an azobenzene species by triggering the reverse isomerization direction (Z → E) by the same wavelength of light, which normally triggers E → Z isomerization. The behavior we report appears to be general, implying that the metastable isomer of a photoswitch can be isomerized to the more stable one catalytically upon reduction, permitting the optimization of azobenzene switching in new as well as indirect ways.

Ultra-low activities of a common radioisotope for permission-free tracking of a drosophilid fly in its natural habitat.

Knowledge of a species’ ecology, including its movement in time and space, is key for many questions in biology and conservation. While numerous tools for tracking larger animals are available, millimetre-sized insects are averse to standard tracking and labelling procedures. Here, we evaluated the applicability of ultra-low, permission-exempt activities of the metastable isomer of the radionuclide Technetium-99 for labelling and field detection of the mountain fly Drosophila nigrosparsa. We demonstrate that an activity of less than 10 MBq is sufficient to label dozens of flies and detect single individuals using standard radiation protection monitors. The methodology presented here is applicable to many small-sized, low-mobility animals as well as independent from light and weather conditions and visual contact with the target organism.

Conformational Contrast of Surface-Mediated Molecular Switches Yields Ångstrom-Scale Spatial Resolution in Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) combines the ability of scanning probe microscopy (SPM) to resolve atomic-scale surface features with the single-molecule chemical sensitivity of surface-enhanced Raman spectroscopy (SERS). Here, we report additional insights into the nature of the conformational dynamics of a free-base porphyrin at room temperature adsorbed on a metal surface. We have interrogated the conformational switch between two metastable surface-mediated isomers of meso-tetrakis(3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP) on a Cu(111) surface. At room temperature, the barrier between the porphyrin ring buckled up/down conformations of the H2TBPP-Cu(111) system is easily overcome, and a 2.6 Å lateral resolution by simultaneous TERS and STM analysis is achieved under ultrahigh vacuum (UHV) conditions. This work demonstrates the first UHV-TERS on Cu(111) and shows TERS can unambiguously distinguish the conformational differences between neighboring molecules with Ångstrom-scale spatial resolution, thereby establishing it as a leading method for the study of metal-adsorbate interactions.

Differing Isomerization Kinetics of Azobenzene-Functionalized Self-Assembled Monolayers in Ambient Air and in Vacuum.

Azobenzenealkanethiols in self-assembled monolayers (SAMs) on Au(111) exhibit reversible trans-cis photoisomerization when diluted with alkanethiol spacers. Using these mixed SAMs, we show switching of the linear optical and second-harmonic response. The effective switching of these surface optical properties relies on a reasonably large cross section and a high photoisomerization yield as well as a long lifetime of the metastable cis isomer. We quantified the switching process by X-ray absorption spectroscopy. The cross sections for the trans-cis and cis-trans photoisomerization with 365 and 455 nm light, respectively, are 1 order of magnitude smaller than in solution. In vacuum, the 365 nm photostationary state comprises 50-74% of the molecules in the cis form, limited by their rapid thermal isomerization back to the trans state. In contrast, the 455 nm photostationary state contains nearly 100% trans-azobenzene. We determined time constants for the thermal cis-trans isomerization of only a few minutes in vacuum and in a dry nitrogen atmosphere but of more than 1 day in ambient air. Our results suggest that adventitious water adsorbed on the surface of the SAM stabilizes the polar cis configuration of azobenzene under ambient conditions. The back reaction rate constants differing by 2 orders of magnitude underline the huge influence of the environment and, accordingly, its importance when comparing various experiments.

A method for imaging and spectroscopy using γ-rays and magnetic resonance.

Magnetic resonance imaging (MRI) provides fine spatial resolution, spectral sensitivity and a rich variety of contrast mechanisms for diagnostic medical applications. Nuclear imaging using γ-ray cameras offers the benefits of using small quantities of radioactive tracers that seek specific targets of interest within the body. Here we describe an imaging and spectroscopic modality that combines favourable aspects of both approaches. Spatial information is encoded into the spin orientations of tiny amounts of a polarized radioactive tracer using pulses of both radio-frequency electromagnetic radiation and magnetic-field gradients, as in MRI. However, rather than detecting weak radio-frequency signals, imaging information is obtained through the detection of γ-rays. A single γ-ray detector can be used to acquire an image; no γ-ray camera is needed. We demonstrate the feasibility of our technique by producing images and spectra from a glass cell containing only about 4 × 10(13) atoms (about 1 millicurie) of the metastable isomer (131m)Xe that were polarized using the laser technique of spin-exchange optical pumping. If the cell had instead been filled with water and imaged using conventional MRI, then it would have contained more than 10(24) water molecules. The high sensitivity of our modality expands the breadth of applications of magnetic resonance, and could lead to a new class of radioactive tracers.

Infrared spectroscopy of water clusters co-adsorbed with hydrogen molecules on a sodium chloride film

Hydrogen gas containing a trace of water vapor was dosed on a vacuum-evaporated sodium chloride film at 13K, and water clusters formed on the substrate were investigated by infrared absorption spectroscopy. Absorption bands due to (H2O)n clusters with n=3–6 and an induced absorption band due to hydrogen were clearly observed. With increasing gas dosage, the intensities of the cluster bands increased linearly while the intensity of the hydrogen band was constant. This suggests that the water clusters were formed in two-dimensional matrices of hydrogen. We found that the water clusters did exist on the surface upon heating even after the hydrogen molecules had desorbed. A further rise of the substrate temperature up to 27K yielded the formation of larger clusters, (H2O)n with n>6. We also discuss the origins of the two bands of the trimer in terms of pseudorotation and a metastable isomer.

Photo-induced linkage NO isomers in the dinitrosyl complex [Ru(NO)2(PCy3)2Cl](BF4) identified by photocrystallography and IR-spectroscopy

Photoinduced metastable linkage NO isomers have been known for a long time in mono-nitrosyl ruthenium or iron transition metal complexes [MLxLy(NO)]n for which appropriate temperature and excitation conditions allow a controlled generation of different metastable states. Dinitrosyl complexes offer attractive possibilities owing to the potential switching of the two nitrosyl ligands, possibly in a selective manner, leading to a complicated and intricated population of metastable states. [Ru(NO)2(PCy3)2Cl]BF4 belongs to a complete series of bis-phosphane complex salts of general formula [Ru(NO)2(PR3)2X](BF4) (X = Cl, Br, I). It presents a square pyramidal geometry with both a linear and a bent NO ligand, and an Ru(d6) electron configuration. Multiple light-induced reversible metastable NO linkage isomers (PLIs) are detected by a combination of photocrystallographic and infrared (IR) analysis. The IR signature of three PLI states has been clearly identified. The structural configuration of the major component (PLI-1) has been derived by X-ray photocrystallography. After irradiation with 405 nm, the orientation of the bent nitrosyl is changed by rotation towards the Cl ligand, opposite to the linear NO. The minor second metastable state (PLI-2) is proposed to result from a side-bonded (similar to MS2 in mono-nitrosyl complexes) state of the linear nitrosyl.

Global picture of isomerization and dissociation of CN2O2: new metastable isomers

A comprehensive potential energy surface of CN2O2, covering 15 new isomers and 30 new transition states was constructed to predict three new observable isomers 14, 22 and 29.

Linkage Isomerization in Nitrosothiols (RSNOs): The X-ray Crystal Structure of an S-nitrosocysteine and DFT Analysis of its Metastable MS1 and MS2 Isomers

Density functional theory calculations reveal that the previously unreported nitrosothiol MS1 and MS2 linkage isomers are metastable species with energies similar to those determined for other experimentally observed XNO linkage isomers.Nitrosation of protein cysteines to yield S-nitrosocysteine (cySNO) is an important component of nitric oxide biology. However, high-resolution structural data of cySNO in the absence of protein environment effects is lacking, as is information on cySNO linkage isomers. We report the ordered X-ray crystal structure of a cySNO compound. We employ density functional theory calculations to probe the ground-state and linkage isomers of cySNO, CH3SNO, and CF3SNO. The HOMO of CH3SNO contains an intramolecular CH···O interaction that helps rationalize the stability of the cis conformation; this interaction is absent in CF3SNO, which favors the trans conformation. We show that the isonitroso MS1 (RSON) and side-on MS2 (RS(η2-ON)) linkage isomers are metastable species, with MS1 and MS2 energies similar to those of other experimentally observed nitroso linkage isomers.

The Nucleation and Growth Mechanism of Thiolate-Protected Au Nanoclusters.

The understanding of the evolution mechanism of thiolate-protected Au nanoclusters from the homoleptic Au(I)-SR clusters to core-stacked ones is crucial for the synthesis of novel thiolated Au clusters. In this work, the global search for a series of "intermediate" Aum(SR)n clusters with m and n ranging from 5 to 12 was implemented by combining basin hopping algorithm, genetic algorithm, and density functional theory (DFT) calculations. Most of Aum(SR)n clusters possess the core-shell structure. Specifically, some typical topologies, such as tetrahedral Au4, triangular bipyramid Au5, octahedral Au6, and vertex-shared Au7, are found to be dominant within the inner core of various clusters. Along with the increase in the number of gold atoms and thiolates, the preliminary nucleation and growth processes of both inner-core and staple-motif protecting units are grouped into three kinds of size evolution routes, i.e., core growth, core dissolution, and staple-motif growth, respectively. Some metastable isomers may also play an important role in the evolution of clusters. The core structures in the lowest-lying isomers and some metastable isomers are similar to the intact or part of the cores found in experimentally detected species. Both the lowest-lying and metastable intermediate clusters may serve as the building block for the further growth. These results rationalize the preliminary nucleation in the "reduction growth" stage, shedding light on the size-evolution mechanism of RS-AuNPs.