Can Anti-Aufbau DFT Calculations Estimate Singlet Excited State Aromaticity? Correspondence on “Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State”

The simple anti-aufbau DFT approach for estimating singlet excited state aromaticity suggested in a recent Communication published in this journal is shown to produce incorrect results because it targets a linear combination of the singlet and triplet configurations involving the HOMO and LUMO rather than the first singlet excited state. If the S₁ state of a molecule is dominated by the HOMO→LUMO excitation, a comparably simple but theoretically consistent and qualitatively correct approximation to the S₁ wavefunction can be achieved by performing a small “two electrons in two orbitals” CASSCF(2,2) calculation which can be followed by the evaluation of magnetic aromaticity criteria such as NICS.     

X-ray Crystallographic Observation of Chiral Transformations within a Metal–Peptide Pore

Porous metal complexes enable single-crystal X-ray crystallographic observation of included guests or reaction intermediates through simple soaking with the guests/substrates. Previous studies on this technique have often encountered difficulties in the observation of chiral structures because the host frameworks had no chirality. We synthesized a new metal–peptide porous complex through a folding-and-assembly strategy and utilized the chiral pore for trapping chiral guests. Chiral alcohols and ketones were successfully included within the pore. Crystallographic analyses clearly revealed not only their chemical structures but also chiral transformation events within the pore such as fixed conformations or an unstable hemiacetal formation.     

Synthesis and Systematic Structural Analysis of Cationic Half-Sandwich Ruthenium Chalcogenocarbonyl Complexes

Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H₂IMes)(CNCH₂Ts)][BAr^F₄] (Cp=η⁵-C₅H₅⁻; H₂IMes=1,3-dimesitylimidazolin-2-ylidene; Ar^F=3,5-(CF₃)₂C₆H₃). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability.     

Application of DEM modified with enlarged particle model to simulation of bead motion in a bead mill

We applied the discrete element method （DEM） of simulation modified by an enlarged particle model to simulate bead motion in a large bead mill. The stainless-steel bead mill has inner diameter of 102 mm and mill length of 198 mm. The bead diameter and filling ratio were fixed respectively at 0.5 mm and 85%. The agitator rotational speed was changed from 1863 to 3261 rpm. The bead motion was monitored experimentally using a high-speed video camera through a transparent mill body. For the simulation, enlarged particle sizes were set as 3-6 mm in diameter. With the DEM modified by the enlarged particle model, the motion of enlarged particles in a mill was simulated.The velocity data of the simulated enlarged particles were compared with those obtained in the experiment. The simulated velocity of the enlarged particles depends on the virtual frictional coefficient in the DEM model. The optimized value of the virtual frictional coefficient can be determined by considering the accumulated mean value. Results show that the velocity of the enlarged particles simulated increases with an increase in the optimum virtual frictional coefficient, but the simulated velocity agrees well with that determined experimentally by optimizing the virtual frictional coefficient in the simulation. The computing time in the simulation decreases with increased particle size.     

Site-Selective C−H Alkenylation of N-Heteroarenes by Ligand-Directed Co/Al and Co/Mg Cooperative Catalysis**

We report herein the design and development of Co/Al and Co/Mg bimetallic catalysts, supported by a phosphine/secondary phosphine oxide (PSPO) bifunctional ligand, for the site-selective C−H alkenylation of nitrogen-containing heteroarenes with alkynes. These catalysts enable the alkenylation of pyridine, pyridone, and imidazo[1,2-a]pyridine derivatives at the C−H site proximal to the Lewis basic nitrogen or oxygen atom, which represents a selectivity profile distinct from that of the previously developed cobalt-diphosphine/aluminum catalyst. The alkenylated products were obtained in moderate to good yields using various heterocycles and differently substituted internal alkynes. Kinetic isotope effect experiments suggest the irreversibility of the C−H activation step, the relevance of which to the rate-limiting step depends on the reaction conditions. Density functional theory calculations indicate that ligand-to-ligand hydrogen transfer is the common mechanism of C−H activation.     

Synthesis of Disaccharide Nucleosides by the O‐Glycosylation of Natural Nucleosides with Thioglycoside Donors

Disaccharide nucleosides constitute an important group of naturally‐occurring sugar derivatives. In this study, we report on the synthesis of disaccharide nucleosides by the direct O‐glycosylation of nucleoside acceptors, such as adenosine, guanosine, thymidine, and cytidine, with glycosyl donors. Among the glycosyl donors tested, thioglycosides were found to give the corresponding disaccharide nucleosides in moderate to high chemical yields with the above nucleoside acceptors using p‐toluenesulfenyl chloride (TolSCl) and silver triflate (AgOTf) as promoters. The interaction of these promoters with nucleoside acceptors was examined by ¹H NMR spectroscopic experiments.     

Highly bent crystals formed by restrained π-stacked columns connected via alkylene linkers with variable conformations

A reproducible formation of strongly bent crystals was accomplished by structurally restraining macrocyclic π-conjugated molecules. The model π-units consist of two 9,10-bis(2-thienylethynyl)anthracenes with a strong propensity for stacking, which are connected in a macrocyclic fashion via two alkylene linkers. The correlation between the crystalline morphology and the macrocyclic structures restrained by a variety of flexible alkylene linker combinations was systematically studied. Bent crystals were obtained only with specific alkylene linkers of appropriate chain length. The alkylene linkers can adopt different conformations in the crystal packing, so as to fill voids within the macrocycle. The ability to form several similar molecular structures with different alkylene conformations gives rise to contaminations of different crystalline phases within a single crystal, and it is these phase contaminations which are responsible for the bending of the crystals.     

Preparation of phthalocyanine-bound myristoyl celluloses for photocurrent generation system

The influences of two structural modifications on the photocurrent generation performance of the Langmuir–Blodgett (LB) film of the 6-O-phthalocyaninyl cellulose derivative were investigated. These structural modifications were the substituent groups at the O-2 and O-3 positions, and the central metal of the phthalocyanine moiety. Specifically, 6-O-Zn/phthalocyaninyl- (8a) and Pd/phthalocyaninyl (8b) -2,3-di-O-myristoylcelluloses were prepared instead of 6-O-Zn/phthalocyaninyl-2,3-di-O-myristylcellulose (2). The LB monolayer film of compound 8a on an indium thin oxide electrode showed higher photocurrent generation performance than that of compound 2. This suggested that myristoyl groups (C-14 acyl groups) were more beneficial to photocurrent generation than myristyl groups (C-14 alkyl groups), as the substituent at the O-2 and O-3 positions. The LB monolayer film of compound 8b showed photocurrent generation from 500 to 700 nm, although a blue-shift in the Q-band maximum was observed. The photocurrent generation performance of compound 8b was significantly higher than that of compound 8a. This indicated that Pd was more beneficial to photocurrent generation than Zn. The film of compound 8b prepared by the horizontal lifting method showed better photocurrent generation performance than that prepared by the vertical dipping method. Consequently, compound 8b is a complementary material to the porphyrin-appended cellulose derivative (1) for photocurrent generation system.