Mechanochromism,Twisted/Folded Structure Determination,and Derivatization of (N‐Phenylfluorenylidene)acridane

(N‐Phenylfluorenylidene)acridane (Ph‐FA) compounds with electron‐withdrawing and ‐donating substituents (H, MeO, Ph, NO₂, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N‐aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p‐NO₂‐C₆H₄‐FA could be crystallographically characterized, which enabled the charge transfer from the electron‐donating acridane moiety to the electron‐accepting fluorenylidene moiety to be understood. Ground‐state mechanochromism, thermochromism, vapochromism, and proton‐induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph‐FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors.     

MOF‐on‐MOF: Oriented Growth of Multiple Layered Thin Films of Metal–Organic Frameworks

The precise alignment of multiple layers of metal–organic framework (MOF) thin films, or MOF‐on‐MOF films, over macroscopic length scales is presented. The MOF‐on‐MOF films are fabricated by epitaxially matching the interface. The first MOF layer (Cu₂(BPDC)₂, BPDC=biphenyl‐4,4′‐dicarboxylate) is grown on an oriented Cu(OH)₂ film by a “one‐pot” approach. Aligned second (Cu₂(BDC)₂, BDC=benzene 1,4‐dicarboxylate, or Cu₂(BPYDC)₂, BPYDC=2,2′‐bipyridine‐5,5′‐dicarboxylate) MOF layers can be deposited using liquid‐phase epitaxy. The co‐orientation of the MOF films is confirmed by X‐ray diffraction. Importantly, our strategy allows for the synthesis of aligned MOF films, for example, Cu₂(BPYDC)₂, that cannot be grown on a Cu(OH)₂ surface. We show that aligned MOF films furnished with Ag nanoparticles show a unique anisotropic plasmon resonance. Our MOF‐on‐MOF approach expands the chemistry of heteroepitaxially oriented MOF films and provides a new toolbox for multifunctional porous coatings.     

Redox-Induced Modulation of Exchange Interaction in a High-Spin Ground-State Diradical/Triradical System

A triplet ground-state diradical molecule, bis(nitronyl nitroxide)-substituted diphenyldihydrophenazine ( 1 ^..), that can be converted into a one-electron oxidized species, 1 ^{… +} , in the quartet ground state has been developed. Surprisingly, these species, 1 ^.. and 1 ^{… +} , can be used under ambient conditions because they are reasonably stable under aerobic conditions, even in solution. The temperature-dependent magnetic susceptibilities reveal that 1 ^.. and 1 ^{… +} are in the triplet state, with a weak exchange interaction (J₁/k_B = +3.1 K) and quartet ground state with a strong exchange interaction (J₂/k_B = +160 K), respectively. The interconversion between the neutral and one-electron oxidized species can be realized through electrochemical reactions. Significantly different absorption bands in the near-IR region newly appeared in the electronic spectra acquired during electrochemical oxidation/reduction.     

Comparison between Abel test stability and thermal decomposition behavior of nitrocellulose

Journal of Thermal Analysis and Calorimetry - Nitrocellulose (NC) is prone to spontaneous decomposition with exothermic heat release and thus is generally evaluated for stability during the storage...     

Micro‐ and Nano‐Liquid Phases Coexistent with Ice as Separation and Reaction Media.

Ice has a variety of scientifically interesting features, some of which have not been reasonably interpreted despite substantial efforts by researchers. Most chemical studies of ice have focused on the elucidation of its physicochemical nature and its roles in the natural environment. Ice often contains impurities, such as salts, and in such cases, a liquid phase coexists with solid ice over a wide temperature range. This impure ice also acts as a cryoreactor, governing the circulation of chemical species of environmental importance. Reactions and phenomena occurring in this liquid phase show features different from those seen in normal bulk aqueous solutions. In the present account, we discuss the chemical characteristics of the liquid phase that develops in a frozen aqueous phase and show how novel analytical systems can be designed based on he features of the liquid phase which are predictable in some cases but unpredictable in others.     

A new <Emphasis Type="Italic">q</Emphasis>-Selberg integral,Schur functions,and Young books

Recently, Kim and Oh expressed the Selberg integral in terms of the number of Young books which are a generalization of standard Young tableaux of shifted staircase shape. In this paper the generating function for Young books according to major index statistic is considered. It is shown that this generating function can be written as a Jackson integral which gives a new q-Selberg integral. It is also shown that the new q-Selberg integral has an expression in terms of Schur functions.     

Dynamic shearing resistance of molten metal films under high pressures and extremely high shearing rates

In the present study plate-impact pressureshear experiments have been conducted to study the dynamic shearing resistance of molten metal films at shearing rates of approximately 10⁷ s⁻¹. These molten films are generated by pressure-shear impact of relatively low melt-point metals such as 7075-T6 Al alloy with high hardness and high flow-strength tool-steel plates. By employing high impact speeds and relatively smooth impacting surfaces, normal interfacial pressures ranging from 1–3 GPa and slip speeds of over 100 m/s are generated during the pressure-shear loading. The resulting friction stress (∼100 to 400 MPa) combined with the high slip speeds generate conditions conductive to interfacial temperatures approaching the fully melt temperature regime of the lower melt-point metal (7075-T6 aluminum alloy) comprising the tribo-pair. During pressure-shear loading, laser interferometry is employed to measure normal and transverse motion at the rear surface of the target plate. The normal component of the particle velocity provides the interfacial normal traction while the transverse component provides the shearing resistance of the interface as it passes through melt. In order to extract the critical interfacial parameters, such as the interfacial slip-speed and interfacial temperatures, a Lagrangian finiteelement code is developed. The computational procedure accounts for dynamic effects, heat conduction, contact with friction, and full thermo-mechanical coupling. At temperatures below melt the flyer and target materials are described as an isotropic thermally softening elastic-viscoplastic solid. For material elements with temperatures in excess of the melt point, a purely Newtonian fluid constitutive model is employed. The results of this hybrid experimental-computational study provide insights into the dynamic shearing resistance of molten metal films at high pressures and extremely high shearing rates.     

Synthesis and Magnetic Properties of (Pyrrolidin‐1‐oxyl)–(Nitronyl Nitroxide)/(Iminonitroxide)‐Dyads

Unlike extensively studied diradicals linked by π‐conjugated systems, only a few studies have investigated weakly coupled diradicals linked by an sp³ carbon atom. Herein, we prepared pyrrolidin‐1‐oxyl–(nitronyl nitroxide)‐dyad 5 and pyrrolidin‐1‐oxyl–iminonitroxide‐dyad 6 . From the observed temperature dependence of the magnetic susceptibility, 5 and 6 were determined to be in singlet ground states with 2J_intra/k_B=?35.2 K and ?13.6 K, respectively. From these results and theoretical calculations of related diradicals, the spin‐polarization model counting the small spin density of the sp³ carbon atom could be used as a spin‐prediction model.