Peripheral Modifications of meso-Hydroxyporphyrins: Formation of π-Electronic Anions and Ion-Pairing Assemblies

Phenyl groups were introduced at the β-positions proximal to the meso-hydroxy moiety in hydroxyporphyrin Ni^II complexes by oxidized BINAP Pd^II complexes. Ion-pairing assemblies of deprotonated π-electronic anions, anionic site of which was stabilized by the introduced phenyl moieties with a bulky cation, were formed. They showed charge-by-charge assemblies, assembly modes of which were modulated by the anionic building units.     

Synthesis of well‐defined block copolymer composed of flexible amphiphilic poly(ethylene glycol) and hydrophobic liquid crystalline segments by living coordination polymerization of allene derivatives and its application to thin film with perpendicularly oriented cylindrical nanostructure

A block copolymer composed of a flexible polar poly(ethylene glycol) (PEG) and a less polar liquid crystalline poly(allene) segments is prepared by the living coordination polymerization of an allene derivative possessing trans‐azobenzene‐containing mesogenic substituent by the use of a π‐allylnickel macroinitiator bearing PEG segment. The thin film of the block copolymer is prepared by the spin coating of its solution onto mica or silicon wafer which proves to possess perpendicularly oriented nanocylindrical microphase separated structures as supported by the differential calorimetric, polarized optical microscopic, grazing‐incidence small‐angle X‐ray scattering, transmission electron microscope, and atomic force microscope measurements.     

Salt‐Free Reduction of Nonprecious Transition‐Metal Compounds: Generation of Amorphous Ni Nanoparticles for Catalytic C–C Bond Formation

A salt‐free procedure for the generation of a wide variety of metal(0) particles, including Fe, Co, Ni, and Cu, was achieved using 2,3,5,6‐tetramethyl‐1,4‐bis(trimethylsilyl)‐1,4‐diaza‐2,5‐cyclohexadiene ( 1 ), which reduced the corresponding metal precursors under mild conditions. Notably, Ni particles formed in situ from the treatment of Ni(acac)₂ (acac=acetylacetonate) with 1 in toluene exhibited significant catalytic activity for reductive C? C bond‐forming reactions of aryl halides in the presence of excess amounts of 1 . By examination of high‐magnification transmission electron microscopy images and electron diffraction patterns, we concluded that amorphous Ni nanoparticles (Ni aNPs) were essential for the high catalytic activity.     

On the exponential Diophantine equation $$(3pm^2-1)^x+(p(p-3)m^2+1)^y=(pm)^z$$

Let m be a positive integer, and let p be a prime with \(p \equiv 1~(\mathrm{mod}~4).\) Then we show that the exponential Diophantine equation \((3pm^2-1)^x+(p(p-3)m^2+1)^y=(pm)^z\) has only the positive integer solution \((x, y, z)=(1, 1, 2)\) under some conditions. As a corollary, we derive that the exponential Diophantine equation \((15m^2-1)^x+(10m^2+1)^y=(5m)^z\) has only the positive integer solution \((x, y, z)=(1, 1, 2).\) The proof is based on elementary methods and Baker’s method.     

Moment convergence of <Emphasis Type="Italic">Z</Emphasis>-estimators

The problem to establish the asymptotic distribution of statistical estimators as well as the moment convergence of such estimators has been recognized as an important issue in advanced theories of statistics. This problem has been deeply studied for M-estimators for a wide range of models by many authors. The purpose of this paper is to present an alternative and apparently simple theory to derive the moment convergence of Z-estimators. In the proposed approach the cases of parameters with different rate of convergence can be treated easily and smoothly and any large deviation type inequalities necessary for the same result for M-estimators do not appear in this approach. Applications to the model of i.i.d. observation, Cox’s regression model as well as some diffusion process are discussed.     

Synthesizing Interpenetrated Triazine-based Covalent Organic Frameworks from CO2

Crystalline triazine-based covalent organic frameworks (COFs) are aromatic nitrogen-rich porous materials. COFs typically show high thermal/chemical stability, and are promising for energy applications, but often require harsh synthesis conditions and suffer from low crystallinity. In this work, we propose an environmentally friendly route for the synthesis of crystalline COFs from CO₂ molecules as a precursor. The mass ratio of CO₂ conversion into COFs formula unit reaches 46.3 %. The synthesis consists of two steps; preparation of 1,4-piperazinedicarboxaldehyde from CO₂ and piperazine, and condensation of the dicarboxaldehyde and melamine to construct the framework. The CO₂-derived COF has a 3-fold interpenetrated structure of 2D layers determined by powder X-ray diffraction, high-resolution transmission electron microscopy, and select-area electron diffraction. The structure shows a high Brunauer–Emmett–Teller surface area of 945 m² g⁻¹ and high stability against strong acid (6 M HCl), base (6 M NaOH), and boiling water over 24 hours. Post-modification of the framework with oxone has been demonstrated to modulate hydrophilicity, and it exhibits proton conductivity of 2.5×10⁻² S cm⁻¹ at 85 °C, 95 % of relative humidity.     

Fine Pore-Structure Engineering by Ligand Conformational Control of Naphthalene Diimide-Based Semiconducting Porous Coordination Polymers for Efficient Chemiresistive Gas Sensing

Exploring new porous coordination polymers (PCPs) that have tunable structure and conductivity is attractive but remains challenging. Herein, fine pore structure engineering by ligand conformation control of naphthalene diimide (NDI)-based semiconducting PCPs with π stacking-dependent conductivity tunability is achieved. The π stacking distances and ligand conformation in these isoreticular PCPs were modulated by employing metal centers with different coordination geometries. As a result, three conjugated PCPs (Co−pyNDI, Ni−pyNDI, and Zn−pyNDI) with varying pore structure and conductivity were obtained. Their crystal structures were determined by three-dimensional electron diffraction. The through-space charge transfer and tunable pore structure in these PCPs result in modulated selectivity and sensitivity in gas sensing. Zn−pyNDI can serve as a room-temperature operable chemiresistive sensor selective to acetone.     

Ruthenium‐Immobilized Periodic Mesoporous Organosilica: Synthesis,Characterization, and Catalytic Application for Selective Oxidation of Alkanes

Periodic mesoporous organosilica (PMO) is a unique material that has a crystal‐like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl₂(CO)₃]₂, is successfully immobilized onto 2,2’‐bipyridine (BPy) units of PMO to form a single‐site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru‐immobilized PMO oxidizes the tertiary C?H bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary C?H bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis‐decalin to cis‐9‐decalol in a 63 % yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions.