Synthesis,Crystal Structure,Electronic Absorption and Magnetic Properties of a Novel Anion-Radical Salt Based on 7,7,8,8-Tetracyanoquinodimethane

Abstract  

A novel anion-radical salt, (AP)(TCNQ)·H₂O (1), where AP = 4-amino-1-butylpyridin-1-ium and TCNQ = 7,7,8,8-tetracyanoquinodimethane, has been synthesized. X-ray single crystal structural analyses show that the TCNQ anions and AP cations form a well-separated stacking column. The TCNQ anions are uniformly spaced to give a one-dimensional (1-D) chain structure through π···π interactions, which is rarely observed in TCNQ anion-radical system. It is noteworthy that compound 1 shows a peculiar magnetic transition from paramagnetism in the high-temperature (HT) phase to spin gap in low-temperature (LT) phase.     

Terminal Redox‐Site Effect on the Long‐Range Electron Conduction of Fe(tpy)2 Oligomer Wires on a Gold Electrode

This article completes our comprehensive understanding of the electron transport properties of our original π‐conjugated redox‐active molecular wires comprising Fe bridged by p‐phenylene linkers (tpy=2,2′:6′,2′′‐terpyridine). The Fe(tpy)₂ oligomer wires comprise three types of tpy ligands: the anchor tpy ligand ( A series) makes a junction between the wire and electrode, the bridging bis‐tpy ligand ( L series) connects the Fe(tpy)₂ units, and the terminal tpy ligand ( T series) possesses a redox site as a probe for the long‐range electron transport ability. Taking advantage of the precise tunability of the composition of the Fe(tpy)₂ oligomer wires, thus far we investigated how A and L impacted on the electron‐transport ability. The excellent long‐range electron transport ability with ultrasmall attenuation constants (β^d, 0.002 Å^?1 as the minimum) depends on L significantly [Chem. Asian J. 2009 , 4, 1361], whereas A is unrelated to the β^d value, but influences the zero‐distance electron‐transfer rate constant, k_et⁰ [J. Am. Chem. Soc. 2010 , 132, 4524]. Herein we study the influence of terminal ligand T ^x (x=1–3). β^d is independent of T , however, T³ , with a cyclometallated Ru complex as the redox site, gives rise to a k_et⁰ value greater than T¹ and T² with ferrocene. This series of simple but definitive conclusions indicates that we have reached the stage of being able to precisely design molecular wires to attain desirable single‐molecule electron conduction.     

Measurement and simulation of the cross sections for the production of 148Gd in thin natW and 181Ta targets irradiated with 0.4- to 2.6-GeV protons

The cross sections for the production of ¹⁴⁸Gd in ^natW and ¹⁸¹Ta targets irradiated by 0.4-, 0.6-, 0.8-, 1.2-, 1.6-, and 2.6-GeV protons at the ITEP accelerator complex have been measured by direct α spectrometry without chemical separation. The experimental data have been compared with the data obtained at other laboratories and with the theoretical simulations of the yields on the basis of the BERTINI, ISABEL, CEM03.02, INCL4.2, INCL4.5, CASCADE07, and PHITS codes.     

Measurement and simulation of the cross sections for nuclide production in 93Nb and natNi targets irradiated with 0.04- to 2.6-GeV protons

The cross sections for nuclide production in thin ⁹³Nb and ^natNi targets irradiated by 0.04- to 2.6-GeV protons have been measured by direct γ spectrometry using two γ spectrometers with the resolutions of 1.8 and 1.7 keV in the ⁶⁰Co 1332-keV γ line. As a result, 1112 yields of radioactive residual nuclei have been obtained. The ²⁷Al(p, x)²²Na reaction has been used as a monitor reaction. The experimental data have been compared with the MCNPX (BERTINI, ISABEL), CEM03.02, INCL4.2, INCL4.5, PHITS, and CASCADE07 calculations.     

Nickel or Palladium‐Catalyzed Decarbonylative Transformations of Carboxylic Acid Derivatives

Carboxylic acid derivatives containing acyl halides, anhydrides, esters, amides and acyl nitriles are highly appealing electrophiles in transition‐metal‐catalyzed carbon‐carbon bond‐forming reactions due to their ready availability and low cost, which can provide divergent transformations of carboxylic acids into other value‐added products. In this Minireview, we focus on the recent advances of decarbonylative transformations of carboxylic acid derivatives in carbon‐carbon bond formations using Ni or Pd catalysts. A series of reaction types, product classifications and reaction pathways are presented herein, which show the advantageous features of carboxylic acid derivatives as alternative to aryl or alkyl halides in terms of reactivity and compatibility. The well‐accepted mechanism of nickel‐ or palladium‐catalyzed decarbonylative transformations involves initial oxidative addition of carboxylic acid derivatives, followed by decarbonylation or transmetalation (or insertion), and reductive elimination to generate the products, thereby regenerating the catalysts.     

Luminescence,Stability, and Proton Response of an Open‐Shell (3,5‐Dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl Radical

A luminescent open‐shell organic radical with high chemical stability was synthesized. (3,5‐Dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl radical (PyBTM) was photoluminescent under various conditions. Fluorescence quantum yields of 0.03, 0.26, and 0.81 (the highest value reported for a stable organic radical) were obtained in chloroform, in poly(methyl methacrylate) film at room temperature, and in an EPA matrix (diethyl ether:isopentane:ethanol) at 77 K, respectively. The photostability of PyBTM is up to 115 times higher than that of the tris(2,4,6‐trichlorophenyl)methyl radical, a previously reported luminescent radical. The pyridine moiety of PyBTM acts as a proton coordination site, thereby allowing for control of the electronic and optical properties of the radical by protonation and deprotonation.     

Magnetic phase transition between ferromagnetic and antiferromagnetic states in Ce(Fe1−xAlx)2

The cubic Laves phase compound Ce(Fe_0.95Al_0.05)₂ exhibits a first order magnetic phase transition from antiferromagnetic to ferromagnetic state at ≈ 100 K with increasing temperature. This note gives the results of the Mössbauer effect of ⁵⁷Fe and the magnetic phase diagram in the external field vs. temperature plane.