Synthesis of Anthracene Derivatives with Azaacene-Containing Iptycene Wings and the Utilization as a Dopant for Solution-Processed Organic Light-Emitting Diodes

Substituted acene derivatives are regarded as promising materials for organic electronic devices such as organic light-emitting diodes (OLEDs). In particular, anthracene derivatives are known to exhibit good fluorescence property, with the air stability and solubility in common organic solvents expected to give advantages for solution-processed device fabrication. In this study, a series of bistriisopropylsilyl(TIPS)ethynyl anthracene derivatives with azaacene-containing iptycene wings have been synthesized by using condensation reactions. Effects of size of azaacenes on optical properties and packing structures were investigated. UV/Vis absorption and fluorescence spectra indicate that the π-elongation of iptycene units has small effects on the overall π-system, which is also supported by electrochemical measurements. Secondly, single-crystal X-ray analysis implies that the molecules likely have interactions with the iptycene units of adjacent molecules, while the iptycene wings and TIPSethynyl groups can prevent the central anthracene unit from undesirable non-radiative energy loss. Finally, the most emissive derivative was used as a dopant for solution-processed OLEDs, showing obvious electroluminescence with a luminance of over 920 cd m⁻².     

The Effect of Viscosity on the Diffusion and Termination Reaction of Organic Radical Pairs

The effect of viscosity on the diffusion efficiency (F_dif) of an organic radical pair in a solvent cage and the termination mechanism, that is, the selectivity of disproportionation (Disp) and combination (Comb) of the geminated caged radical pair and the diffused radicals encountered, were investigated quantitatively by following the photolysis of dimethyl 2,2′-azobis(2-methylpropionate) (V-601) in the absence and presence of PhSD. F_dif and Disp/Comb selectivity outside the cage [Disp_(dif)/Comb_(dif)] are highly sensitive to the viscosity. In contrast, the Disp/Comb selectivity inside the cage [Disp_(cage)/Comb_(cage)] is rather insensitive. The difference in viscosity dependence between Disp_(cage)/Comb_(cage) and Disp_(dif)/Comb_(dif) is explained by the spin state of the radical pair inside and outside the cage and the spin state dependent configurational changes of the radical pair upon their collision. Given that the configurational change of the radicals associates the displacement and reorganization of solvents around the radicals, the termination outside the cage, which requires larger change than that inside the cage, is highly viscosity dependent. Furthermore, while the bulk viscosity of each solvent shows good correlation with F_dif and Disp/Comb selectivity, microviscosity is the better parameter predicting F_dif and Disp_(dif)/Comb_(dif) selectivity regardless of the solvents.     

A Theoretical study on the charge and discharge states of Na-ion battery cathode material,Na1+xFePO4F

Na₂FePO₄F is a promising cathode material for a Na-ion battery because of its high electronic capacity and good cycle performance. In this work, first principle calculations combined with cluster expansion and the Monte Carlo method have been applied to analyze the charge and discharge processes of Na₂FePO₄F by examining the voltage curve and the phase diagram. As a result of the density functional theory calculation and experimental verification with structural analysis, we found that the most stable structure of Na_1.5FePO₄F has the P2₁/b11 space group, which has not been reported to date. The estimated voltage curve has two clear plateaus caused by the two-phase structure composed of P2₁/b11 Na_1.5FePO₄F and Pbcn Na₂FePO₄F or Na₁FePO₄F and separated along the c-axis direction. The phase diagram shows the stability of the phase-separated structure. Considering that Na₂FePO₄F has diffusion paths in the a- and c-axis directions, Na₂FePO₄F has both innerphase and interphase diffusion paths. We suggest that the stable two-phase structure and the diffusion paths to both the innerphase and interphases are a key for the very clear plateau. We challenge to simulate a nonequilibrium state at high rate discharge with high temperature by introducing a coordinate-dependent chemical potential. The simulation shows agreement with the experimental discharge curve on the disappearance of the two plateaus. © 2018 Wiley Periodicals, Inc.     

A new periodic pattern with five‐neighbored domain packing from ABC triblock terpolymer/B homopolymer blend

Self‐assembled structures from poly(isoprene‐b‐styrene‐b‐2‐vinylpyridine)(ISP)/styrene homopolymer blend were investigated. Five terpolymers whose total molecular weight, M, is in the narrow range of 121k < M < 214k, and volume fractions of the center block polystyrenes, ?_S, are similar at around 0.55, were prepared as parent block terpolymers. Their ?_P/?_I ratios, used as an indicator of asymmetry, are varied in the range 0.32 < ?_P/?_I < 2.46. Three low‐molecular weight styrene homopolymers with molecular weights of 3k, 9k, and 12k, respectively, were mixed with those block terpolymers to produce blends with almost constant styrene content within the range 0.65 < ?_S < 0.68. Both ISP/S(3k) and ISP/S(12k) blend series show a morphological transition from tetragonally packed cylinders (TPC) to double hexagonal structure (DHS) with hexagonally arrayed polyisoprene cylinders, each surrounded by six thin cylinders as satellites. If one focuses on ISP‐III(150k)/S blends whose ?_P/?_I is 0.88, TPC for ISP‐III/S(3k) was transformed to DHS for ISP‐III/S(12k), evidently due to the molecular weight effect of the added homopolymer. Finally a new periodic pattern, having P cylinders surrounded by five I cylinders each, has been discovered from ISP‐III/S(9k) at overall composition of ?_I/?_S/?_P = 0.17/0.68/0.15 and polystyrene block/styrene homopolymer ratio of w_S(b)/w_S(h) = 1.4. This structure was confirmed to possess hexagonal symmetry with larger unit cell than regular patterns ever known by X‐ray diffraction experiment. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 907–911     

Aromaticity Relocation in Perylene Derivatives upon Two‐Electron Oxidation To Form Anthracene and Phenanthrene

We prepared perylene dications 1 ²⁺ and 2 ²⁺ by using “capped” perylene derivatives, and for the first time, successfully obtained single crystals of a perylene dication 1 ²⁺ that enabled us to perform its structural analysis. We realized that the substituted aryl groups on perylene control the positions of positive charges, thus the remaining electronic system satisfies Clar's sextet rule toward the highest number of localized sextets. Experimental and theoretical evidence proved that Clar's aromatic π‐sextet rule could be applied even for the dicationic perylenes in a very simple way.     

Synthesis of C12-Keto Saxitoxin Derivatives with Unusual Inhibitory Activity Against Voltage-Gated Sodium Channels

A novel series of C12-keto-type saxitoxin (STX) derivatives bearing an unusual nonhydrated form of the ketone at C12 has been synthesized, and their Na_V-inhibitory activity has been evaluated in a cell-based assay as well as whole-cell patch-clamp recording. Among these compounds, 11-benzylidene STX ( 3 a ) showed potent inhibitory activity against neuroblastoma Neuro 2A in both cell-based and electrophysiological analyses, with EC₅₀ and IC₅₀ values of 8.5 and 30.7 nm , respectively. Interestingly, the compound showed potent inhibitory activity against tetrodotoxin-resistant subtype of Na_V1.5, with an IC₅₀ value of 94.1 nm . Derivatives 3 a – d and 3 f showed low recovery rates from Na_V1.2 subtype (ca 45–79 %) compared to natural dcSTX ( 2 ), strongly suggesting an irreversible mode of interaction. We propose an interaction model for the C12-keto derivatives with Na_V in which the enone moiety in the STX derivatives 3 works as Michael acceptor for the carboxylate of Asp¹⁷¹⁷.     

Alkane Shape- and Size-Recognized Selective Vapor Sorption in “Channel-Like” Crystals Based on Thiacalixarene Assemblies

Alkanes composed of C−C and C−H show a low electric polarization, and therefore, there is only very weak interaction between alkanes and adsorbents. Thus, it is difficult to separate a specific alkane from a mixture of alkanes by adsorption. Here, two activated “channel-like” crystals generated from brominated thiacalix[4]arene propyl ethers, which adopt 1,3-alternate and partial cone conformations, recognize specific alkane vapors depending on alkane-shape and -size, sorting in three-type alkane guests such as linear, branched, and cyclic alkanes. Two activated crystals, which are prepared by removal of solvent upon heating under reduced pressure, incorporate branched and/or cyclic alkane vapors by a unique “gate-opening” mechanism via a crystal transformation in the process. Linear alkane vapors do not trigger gate opening and are not taken up by the activated crystals. The shape and size molecular-recognition properties of the activated crystals promises considerable usefulness for the separation of linear, branched, and cyclic alkanes.     

Visible-Light-Induced Heptacene Generation under Ambient Conditions: Utilization of Single-crystal Interior as an Isolated Reaction Site

The photo-induced generation of unstable molecules generally requires stringent conditions to prevent oxidation and the concomitant decomposition of the products. The visible-light-induced conversion of two heptacene precursors to heptacene was studied. Single crystals of bis- and mono-α-diketone-type heptacene precursors ( 7-DK2 and 7-DK1 , respectively), were prepared to investigate the effect of precursor structure on reactivity. The photoirradiation of a 7-DK2 single crystal cleaved only one α-diketone group, forming an intermediate bearing a pentacene subunit, while that of a 7-DK1 single crystal gave rise to characteristic absorption peaks of heptacene and their increase in intensity with photoirradiation time, indicating the generation of heptacene without decomposition. Heptacene production was not observed when the precursors were photoirradiated in solution, implying that the single crystal interior provided isolation from the external environment, thus preventing heptacene oxidation.