Electronic circular dichroism spectrum of uridine studied by the SAC-CI method

Abstract Symmetry-adapted cluster-configuration interaction (SAC-CI) method was applied to calculate electronic CD spectrum of a nucleoside, uridine. Based on the theoretical CD and absorption spectra, the observed peaks in the experimental spectra were assigned. The excited states of uracil, the base part of uridine, were also calculated for comparison. The origin of CD rotational strength for the lowlying p-p * and n-p * excited states was analyzed. Rotational strength of the p-p * transition depends on the magnitude of the electric and magnetic transition dipole moments, while that of the n-p * originates from the angle between the two transition moments

The outer valence ionization energies of thiazyl cyanide

We present a theoretical ab initio investigation of the low-energy valence Photo Electron (PE) spectrum of NSCN, a novel thiazyl compound recently synthetized, by using many-body post-SCF electronic structure methods. To account for correlation and relaxation effects neglected within the Koopmanns' theorem approximation, we used the SAC/SAC-C. I. theory in calculating the lowest ionization energies. Correlation effects are quite important to reliably understand the recorded PE intensity of NSCN. We are able to propose a different assignment of the entire outer valence PE spectrum of NSCN which seems more consistent and in better agreement with the experiment. We also discuss similarities and differences in the ionization energies of NSCN and closely related molecules (cyanogen and thiazyl halides)

Aluminum porphyrins with quaternary ammonium halides as catalysts for copolymerization of cyclohexene oxide and CO2: metal–ligand cooperative catalysis

Bifunctional AlIII porphyrins with quaternary ammonium halides, 2-Cl and 2-Br, worked as excellent catalysts for the copolymerization of cyclohexene oxide (CHO) and CO2 at 120 °C. Turnover frequency (TOF) and turnover number (TON) reached 10 000 h−1 and 55 000, respectively, and poly(cyclohexene carbonate) (PCHC) with molecular weight of up to 281 000 was obtained with a catalyst loading of 0.001 mol%. In contrast, bifunctional MgII and ZnII counterparts, 3-Cl and 4-Cl, as well as a binary catalyst system, 1-Cl with bis(triphenylphosphine)iminium chloride (PPNCl), showed poor catalytic performances. Kinetic studies revealed that the reaction rate was first-order in [CHO] and [2-Br] and zero-order in [CO2], and the activation parameters were determined: ΔH‡ = 12.4 kcal mol−1, ΔS‡ = −26.1 cal mol−1 K−1, and ΔG‡ = 21.6 kcal mol−1 at 80 °C. Comparative DFT calculations on two model catalysts, AlIII complex 2′ and MgII complex 3′, allowed us to extract key factors in the catalytic behavior of the bifunctional AlIII catalyst. The high polymerization activity and carbonate-linkage selectivity originate from the cooperative actions of the metal center and the quaternary ammonium cation, both of which facilitate the epoxide-ring opening by the carbonate anion to form the carbonate linkage in the key transition state such as TS3b (ΔH‡ = 13.3 kcal mol−1, ΔS‡ = −3.1 cal mol−1 K−1, and ΔG‡ = 14.4 kcal mol−1 at 80 °C)

A boron-transfer mechanism mediating the thermally induced revival of frustrated carbene–borane pairs from their shelf-stable adducts

Chemists have designed strategies that trigger the conformational isomerization of molecules in response to external stimuli, which can be further applied to regulate the complexation between Lewis acids and bases. We have recently developed a system in which frustrated carbene–borane pairs are revived from shelf-stable but external-stimuli-responsive carbene–borane adducts comprised of N-phosphine-oxide-substituted imidazolylidenes (PoxIms) and triarylboranes. Herein, we report the detailed mechanism on this revival process. A thermally induced borane-transfer process from the carbene carbon atom to the N-phosphinoyl oxygen atom initiates the transformation of the carbene–borane adduct. Subsequent conformational isomerization via the rotation of the N-phosphinoyl group in PoxIm moieties eventually leads to the revival of frustrated carbene–borane pairs that can cleave H2. We believe that this work illustrates an essential role of dynamic conformational isomerization in the regulation of the reactivity of external-stimuli-responsive Lewis acid-base adducts that contain multifunctional substituents.Hoshimoto Y., Sakuraba M., Kinoshita T., et al. A boron-transfer mechanism mediating the thermally induced revival of frustrated carbene–borane pairs from their shelf-stable adducts. Communications Chemistry 4, 137 (2021); https://doi.org/10.1038/s42004-021-00576-1

Doubly linked chiral phenanthrene oligomers for homogeneously π-extended helicenes with large effective conjugation length

Helically twisted conductive nanocarbon materials are applicable to optoelectronic and electromagnetic molecular devices working on the nanometer scale. Herein, we report the synthesis of per-peri-perbenzo[5]- and [9]helicenes in addition to previously reported π-extended [7]helicene. The homogeneously π-extended helicenes can be regarded as helically fused oligo-phenanthrenes. The HOMO−LUMO gap decreased significantly from 2.14 to 1.15 eV with increasing helical length, suggesting the large effective conjugation length (ECL) of the π-extended helical framework. The large ECL of π-extended helicenes is attributed to the large orbital interactions between the phenanthrene subunits at the 9- and 10-positions, which form a polyene-like electronic structure. Based on the experimental results and DFT calculations, the ultrafast decay dynamics on the sub-picosecond timescale were attributed to the low-lying conical intersection

The JCMT BISTRO Survey: Studying the Complex Magnetic Field of L43

We present observations of polarized dust emission at 850 μm from the L43 molecular cloud, which sits in the Ophiuchus cloud complex. The data were taken using SCUBA-2/POL-2 on the James Clerk Maxwell Telescope as a part of the BISTRO large program. L43 is a dense (NH 10 22 2 ~ –1023 cm−2) complex molecular cloud with a submillimeter-bright starless core and two protostellar sources. There appears to be an evolutionary gradient along the isolated filament that L43 is embedded within, with the most evolved source closest to the Sco OB2 association. One of the protostars drives a CO outflow that has created a cavity to the southeast. We see a magnetic field that appears to be aligned with the cavity walls of the outflow, suggesting interaction with the outflow. We also find a magnetic field strength of up to ∼160 ± 30 μG in the main starless core and up to ∼90 ± 40 μG in the more diffuse, extended region. These field strengths give magnetically super- and subcritical values, respectively, and both are found to be roughly trans-Alfvénic. We also present a new method of data reduction for these denser but fainter objects like starless cores

Filamentary Network and Magnetic Field Structures Revealed with BISTRO in the High-Mass Star-Forming Region NGC2264 : Global Properties and Local Magnetogravitational Configurations

We report 850 $\mu$m continuum polarization observations toward the filamentary high-mass star-forming region NGC 2264, taken as part of the B-fields In STar forming Regions Observations (BISTRO) large program on the James Clerk Maxwell Telescope (JCMT). These data reveal a well-structured non-uniform magnetic field in the NGC 2264C and 2264D regions with a prevailing orientation around 30 deg from north to east. Field strengths estimates and a virial analysis for the major clumps indicate that NGC 2264C is globally dominated by gravity while in 2264D magnetic, gravitational, and kinetic energies are roughly balanced. We present an analysis scheme that utilizes the locally resolved magnetic field structures, together with the locally measured gravitational vector field and the extracted filamentary network. From this, we infer statistical trends showing that this network consists of two main groups of filaments oriented approximately perpendicular to one another. Additionally, gravity shows one dominating converging direction that is roughly perpendicular to one of the filament orientations, which is suggestive of mass accretion along this direction. Beyond these statistical trends, we identify two types of filaments. The type-I filament is perpendicular to the magnetic field with local gravity transitioning from parallel to perpendicular to the magnetic field from the outside to the filament ridge. The type-II filament is parallel to the magnetic field and local gravity. We interpret these two types of filaments as originating from the competition between radial collapsing, driven by filament self-gravity, and the longitudinal collapsing, driven by the region's global gravity.Comment: Accepted for publication in the Astrophysical Journal. 43 pages, 32 figures, and 4 tables (including Appendix

Filamentary Network and Magnetic Field Structures Revealed with BISTRO in the High-mass Star-forming Region NGC 2264: Global Properties and Local Magnetogravitational Configurations

We report 850 μm continuum polarization observations toward the filamentary high-mass star-forming region NGC 2264, taken as part of the B-fields In STar forming Regions Observations large program on the James Clerk Maxwell Telescope. These data reveal a well-structured nonuniform magnetic field in the NGC 2264C and 2264D regions with a prevailing orientation around 30° from north to east. Field strength estimates and a virial analysis of the major clumps indicate that NGC 2264C is globally dominated by gravity, while in 2264D, magnetic, gravitational, and kinetic energies are roughly balanced. We present an analysis scheme that utilizes the locally resolved magnetic field structures, together with the locally measured gravitational vector field and the extracted filamentary network. From this, we infer statistical trends showing that this network consists of two main groups of filaments oriented approximately perpendicular to one another. Additionally, gravity shows one dominating converging direction that is roughly perpendicular to one of the filament orientations, which is suggestive of mass accretion along this direction. Beyond these statistical trends, we identify two types of filaments. The type I filament is perpendicular to the magnetic field with local gravity transitioning from parallel to perpendicular to the magnetic field from the outside to the filament ridge. The type II filament is parallel to the magnetic field and local gravity. We interpret these two types of filaments as originating from the competition between radial collapsing, driven by filament self-gravity, and longitudinal collapsing, driven by the region's global gravity

The JCMT BISTRO Survey: Studying the Complex Magnetic Field of L43

We present observations of polarized dust emission at 850 μm from the L43 molecular cloud, which sits in the Ophiuchus cloud complex. The data were taken using SCUBA-2/POL-2 on the James Clerk Maxwell Telescope as a part of the BISTRO large program. L43 is a dense ( NH2∼1022 –1023 cm−2) complex molecular cloud with a submillimeter-bright starless core and two protostellar sources. There appears to be an evolutionary gradient along the isolated filament that L43 is embedded within, with the most evolved source closest to the Sco OB2 association. One of the protostars drives a CO outflow that has created a cavity to the southeast. We see a magnetic field that appears to be aligned with the cavity walls of the outflow, suggesting interaction with the outflow. We also find a magnetic field strength of up to ∼160 ± 30 μG in the main starless core and up to ∼90 ± 40 μG in the more diffuse, extended region. These field strengths give magnetically super- and subcritical values, respectively, and both are found to be roughly trans-Alfvénic. We also present a new method of data reduction for these denser but fainter objects like starless cores