Discrete dihedral-angle modulation in porphyrin wheels adsorbed on Cu(1 0 0) observed by scanning tunneling microscopy

Conformations of two dodecameric porphyrin wheels adsorbed on a Cu(1 0 0) were probed by using scanning tunneling microscopy (STM). Whereas a wheel consisting of six meso-meso linked diporphyrins was detected as uniform ring structure, several different images with three discrete molecular heights were detected for a wheel consisting of six meso-meso, β-β,β-β triply-linked planar diporphyrins. These results indicate that the former has a conformation similar to that in a free space, while the latter has various conformations with respect to orientation of planar diporphyrin units toward the metal surface. Several discrete STM images of the latter have been interpreted in terms of possible eight conformations, which vary as to relative orientation of neighboring diporphyrin units.     

Optically induced mechanical interaction between semiconductor quantum dots under an electronic resonance condition

Assuming an electronic resonance condition, we study the shape-dependence of the radiation force (RF) on a semiconductor quantum dot (QD) floating in medium and the optically induced mechanical interaction (OIMI) between two QDs with Maxwell stress tensor (MST) method, where the response fields are calculated by the improved discrete dipole approximation (DDA). Main results are as follows: (1) Properties of the RF on an isolated QD drastically change due to its shape and polarization of an incident light, which can be used for shape-selective manipulation. (2) Anomalous OIMI between two QDs arises depending on the spatial structures of internal fields, which results from the interaction between polarizations in respective QDs when they are near each other.     

Formal Synthesis of Sarain A: Intramolecular Cycloaddition of an Eight‐Membered Cyclic Nitrone to Construct the 2‐Azabicyclo[3.3.1]nonane Framework

An enantioselective route to the tetracyclic skeleton of sarain A has been developed. Asymmetric reduction of an ynone introduced a chiral center which was transferred to the contiguous tertiary stereogenic centers through an Ireland–Claisen rearrangement. The 2‐azabicyclo[3.3.1]nonane framework was constructed by an unprecedented intramolecular cycloaddition of an eight‐membered cyclic nitrone. Using the steric bias of the bicyclic system, the quaternary carbon atom was constructed by a stereoselective aldol reaction. Further ring formations were performed by ring‐closing metathesis for the 13‐membered ring and an iodoamidation reaction for the pyrrolidine ring. The present synthesis has successfully provided an alternative route to the late‐stage intermediate of Overman’s synthesis.     

Hydrogen Production from a Methanol–Water Solution Catalyzed by an Anionic Iridium Complex Bearing a Functional Bipyridonate Ligand under Weakly Basic Conditions

An efficient catalytic system for the production of hydrogen from a methanol–water solution has been developed using a new anionic iridium complex bearing a functional bipyridonate ligand as a catalyst. This system can be operated under mild conditions [weakly basic solution (0.046 mol L^?1 NaOH) below 100 °C] without the use of an additional organic solvent. Long‐term continuous hydrogen production from a methanol–water solution catalyzed by the anionic iridium complex was also achieved.     

A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State

Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual C? N bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor.     

A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf‐Stable Carbene Borane Complexes

N‐Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C₆F₅)₃ depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions were successfully controlled by tuning the strain in the PoxIm–B(C₆F₅)₃ complexes so that reactivation only occurred above ambient temperature.     

Total Synthesis and Biological Evaluation of the Antibiotic Lysocin E and Its Enantiomeric,Epimeric, and N‐Demethylated Analogues

Lysocin E, a macrocyclic peptide, exhibits potent antibacterial activity against methicillin‐resistant Staphylococcus aureus (MRSA) through a novel mechanism. The first total synthesis of lysocin E was achieved by applying a full solid‐phase strategy. The developed approach also provides rapid access to the enantiomeric, epimeric, and N‐demethylated analogues of lysocin E. Significantly, the antibacterial activity of the unnatural enantiomer was comparable to that of the natural isomer, suggesting the absence of chiral recognition in its mode of action.     

Belt‐Shaped Cyclonaphthylenes

The recent development of cyclo‐para‐phenylenes has demonstrated the feasibility of radial π systems in nanohoop structures, especially in the crystalline state. However, in contrast to macrocyclic molecules with benzene units, which have a several‐decades‐long history, macrocycles composed solely of naphthylene units (the smallest acene) have been much less explored. Although two examples of cyclonaphthylenes have been reported to date, neither possesses a radial π system. We herein report the first example of belt‐shaped cyclonaphthylenes with curved π systems. The molecule, [8]cyclo‐amphi‐naphthylene, is linked at the 2,6‐positions of the naphthylene units, thus affording belt‐shaped molecules. Although the molecular structures are flexible, which allows for rotation of the naphthylene units in solution, they can be rigidified with the aid of methylene bridges to afford persistent molecular structures in solution.     

A remark on boundary level admissible representations

We point out that it is immediate by our character formula that in the case of a boundary level the characters of admissible representations of affine Kac–Moody algebras and the corresponding W-algebras decompose in products in terms of the Jacobi form ${?}_{11}(\tau ,z)$.     

Production of secondary drops during the single water drop impact onto a plane water surface

The normal impact of single water drops onto a plane water surface was studied experimentally to reveal the amount of secondary drops produced from the rim of crown-like interfacial structure. Within the experimental ranges tested, the ratio of the total mass of secondary drops to the mass of primary drop was approximately within 0–1 and correlated well as the function of dimensionless parameter K that consisted of the impact Weber number We and the Ohnesorge number Oh (K = We Oh ^−0.4). The dependences of the number and the mean diameter of secondary drops on K and dimensionless film thickness were also investigated.