Layered [3.3]Orthocyclophane Tricarbonylchromium Complexes

The preparation of the layered [3.3]orthocyclophane tricarbonylchromium mono- and bis complexes, 4 and 5 , are described. X-ray crystallographic analysis reveals the fact that the distances and the dihedral angle between the planes of the two benzo rings in mono complex 4 decrease as compared to those in 1 . This is due to the decrease in π electron density in one benzo unit.     

Enantiomerically Pure Cyclic trans-1,2-Diols,Diamines, and Amino Alcohols by Intramolecular Pinacol Coupling of Planar Chiral Mono-Cr(CO)3 Complexes of Biaryls

Without any formation of stereoisomers , the intramolecular pinacol cyclization of 1 —planar chiral mono-Cr(CO)₃ complexes of 1,1′-biphenyls with carbonyl functionalities at the 2- and 2′-positions—with samarium diiodide gives cyclic trans-1,2-diols 2 . Upon exposure to sunlight, the chromium-complexed diols 2 produce optically pure chromium-free trans-diols 3 . Similarly, the corresponding enantiomerically pure trans-1,2-diamines and amino alcohols are obtained from the planar chiral chromium complexes of biphenyls with diimino or keto-imino functionalities. R¹=H, OMe; R²=H, Me; R³=H, Me.     

Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis

Improved methods for the synthesis of linear and cyclic poly(diphenylacetylene)s by polymerization of the corresponding diphenylacetylenes using MoCl₅- and WCl₄-based catalytic systems have been developed. MoCl₅ induces migratory insertion polymerization of diphenylacetylenes in the presence of arylation reagents such as Ph₄Sn and ArSnⁿBu₃ to produce cis-stereoregular linear poly(diphenylacetyelene)s with high molecular weights (number-average molar mass (M_n)=30,000–3,200,000) in good yields (up to 98 %). On the other hand, WCl₄ induces ring expansion polymerization of diphenylacetylenes in the presence of Ph₄Sn or reducing reagents to produce cis-stereoregular cyclic poly(diphenylacetylene)s with high molecular weights (M_n=20,000–250,000) in moderate to good yields (up to 90 %). Both catalytic systems are applicable to the polymerization of various diphenylacetylenes having polar functional groups such as esters that are not efficiently polymerized by conventional methods using WCl₆-Ph₄Sn and TaCl₅-ⁿBu₄Sn systems.     

Synthesis of porous C/Fe3O4 microspheres by spray pyrolysis with NaNO3 additive for lithium-ion battery applications

In this work, we successfully synthesized porous C/Fe₃O₄ microspheres by spray pyrolysis at 700ºC with a sodium nitrate (NaNO₃) additive in the precursor solution. Furthermore, we studied their electrochemical properties as anode material for Li-ion batteries. The systematic studies by various characterization techniques show that NaNO₃ catalyzes the carbonization of sucrose and enhances the crystallization of Fe₃O₄. Moreover, an aqueous etching can easily remove sodium compounds to produce porous C/Fe₃O₄ microspheres with large surface areas and pore volumes. The porous C/Fe₃O₄ microspheres exhibit a reversible capacity of ~780 mAh g^–1 in the initial cycles and ~520 mAh g^–1 after 30 cycles at a current density of 50 mA g^–1. Moreover, a reversible capacity of ~400 mAh g^–1 is attainable after 200 cycles, even at a high current density of 500 mA g^–1. The wide range of pores produced from the removal of sodium compounds might enable easy electrolyte penetration and facilitate fast Li-ion diffusion, while the N-doping can promote the electronic conductivity of the carbon. These features of porous C/Fe₃O₄ microspheres led to the improved electrochemical properties of this sample.

Graphical Abstract

     

Changes in the Hydration State of a Block Copolymer of Poly(N‐isopropylacrylamide) and Poly(ethylene oxide) on Thermosensitive Micellization in Water

A diblock copolymer of poly(N‐isopropylacrylamide) and poly(ethylene oxide) (PiPA‐b‐PEO) has been prepared by radical polymerization with a ceric ion initiation system. Its thermosensitive micellization has been investigated by means of IR and fluorescence spectroscopy. The PiPA segments are critically dehydrated above 33.5°C (5 wt.‐%) and associate through hydrophobic interaction to form the hydrophobic core of the micelle. In contrast, the change in the hydration state of the PEO segments upon micellization is small.