The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

加权二次有理Bézier插值曲线

在本文中,给定一组有序空间数据点列及每个数据点的切矢向量,利用加权二次有理Bézier曲线对数据点作插值曲线,使该曲线具有C1连续性,并且权因子只是对相应顶点曲线附近产生影响,同调整两个相邻的权因子可以调整这两个相邻顶点之间的曲线和它的控制多边形.     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Buckling of a stiff thin film on a compliant substrate in large deformation

A finite-deformation theory is developed to study the mechanics of thin buckled films on compliant substrates. Perturbation analysis is performed for this highly nonlinear system to obtain the analytical solution. The results agree well with experiments and finite element analysis in wavelength and amplitude. In particular, it is found that the wavelength depends on the strain. Based on the accurate wavelength and amplitude, the membrane and peak strains in thin films, and stretchability and compressibility of the system are also obtained analytically.     

Synthesis and structural characterization of novel,fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties

The synthesis and structural characterization of a series of novel, fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties are described. The monomers, 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a – 2d ), were conveniently and efficiently synthesized from phenols and phthalic anhydride in two steps via 2‐(4′‐hydroxybenzoyl)benzoic acids, which were first obtained by the Friedel–Crafts reaction in good yields and with high stereoselectivity and were then converted into 2a – 2d by fusion with hydrazine. All the polymers were prepared by nucleophilic aromatic substitution (S_NAr) polycondensation between the compounds perfluorobiphenyl and 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a ‐ 2d ). The resulting fluorinated polymers were readily soluble in common organic solvents (e.g., CHCl₃, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N‐methylpyrrolidone, etc.) at room temperature. Their weight‐average molecular weights and the polydispersities ranged from (7.96–18.25) × 10³ to 1.31–2.71, respectively. Their glass‐transition temperatures varied from 213 to 263 °C. They were all stable up to 390 °C both in air and in argon. The 5% weight‐loss temperatures of these polymers in air and argon ranged from 393–487 to 437–509 °C, respectively. Wide‐angle X‐ray diffraction studies indicated they were all amorphous and could be attributed to the presence of kink nonplanar moiety, phenyl phthalazinone along the polymer backbone. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 925–932, 2004     

Reversible nonlinear conduction in high‐density polyethylene/acetylene carbon black composites at various ambient temperatures

The reversible nonlinear conduction (RNC) in of high‐density polyethylene/acetylene carbon black composites with different degrees of crosslinking was studied above room temperature and below the melting point of high‐density polyethylene (HDPE). The experimental current density‐electric field strength curves can be overlapped onto a master curve, suggesting that the microscopic mechanisms for the appearance of RNC exist regardless of the ambient temperature and the crosslinking degree of the HDPE matrix. The relationship between the crossover current density and the linear conductivity can be explained in the framework of the dynamic random‐resistor‐network model. According to these results, two electron‐tunneling models are suggested to interpret the microscopic conduction behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1212–1217, 2004     

Crystal and molecular structure of (μ-p-CH3C6H4C2S) (μ-n-C3H7S)Fe2(CO)6Co2(CO)6

The crystal and molecular structure of the complex containing cobalt-carbon and iron-sulfur cluster cores, (μ-p-CH₃C₆H₄C₂S) (μ-n-C₃H₇S)Fe₂(CO)₆Co₂(CO)₆, has been determined by X-ray diffraction method. The crystals are triclinic, space group P&1bar;, with a — 9.139(2), b=9.610(1), c-17.183(2) Å, α = 84.36(1), β-89.45(1), γ=88.15(1)°, V-1501.0 ų; Z=2, D_c=1.74 g/cm³. R=0.072, Rw=0.081. The results of the structure determination show a cobalt-carbon cluster core formed through the reaction of (μ-p-CH₃C₆H₄C₂S)(μ-n-C₃H₇S)Fe₂(CO)₆ with Co₂(CO)₈. In the cobalt-carbon cluster core, the bond length of the original C≡C lengthened to 1.324 Å which is close to the typical value of carbon-carbon double bond. The groups connecting the carbons of the cluster core are in cis position and lie on the opposite side of cobalt atoms. In this complex, the conformation of —SC₃H₇ is e-type, while that of —SC₂C₆H₄CH₃ is a-type.     

Single-molecule single crystals

Various approaches to the preparation and verification of single-molecule single crystals are discussed for polyethylene and poly (oxyethylene). Analytic tools are electron microscopy, electron diffraction, and differential scanning calorimetry. The main difficulty in producing a single-molecule single crystal is to keep crystals from joining during growth.     

Competitive influence of atactic polystyrene and supercritical carbon dioxide on the conformation of syndiotactic polystyrene

The crystallization behavior of miscible syndiotactic polystyrene (sPS) and atactic polystyrene (aPS) blends with different sPS/aPS weight ratios was investigated in supercritical CO₂ by using Fourier‐transform infrared spectroscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Supercritical CO₂ and aPS exhibited different effects on the conformational change of sPS and competed with each other. Increasing the content of amorphous aPS in the blends made its effect on the conformational change of sPS gradually surpass that of supercritical CO₂. Supercritical CO₂ favored the formation of the helical conformation of sPS in lower temperature range and the all trans planar conformation in higher temperature range, instead of forming the latter one only in higher temperature range in ambient atmosphere. However, increasing aPS content in the blends pushed the range for forming the helical conformation to lower temperature and made the all trans planar conformation dominant in aPS/sPS 25/75 blend after treating in supercritical CO₂ above 60 °C. The all trans planar zigzag conformation was more favorable than the helical conformation after mixing aPS in sPS in supercritical CO₂. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1755–1764, 2007