Novel metal-organic frameworks with specific topology from new tripodal ligands: 1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene

Reactions of two new tripodal ligands 1,3,5-tris(1-imidazolyl)benzene (4) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (5) with metal [Ag(I), Cu(II), Zn(II), Ni(II)] salts lead to the formation of novel two-dimensional (2D) metal-organic frameworks [Ag(2)(4)(2)][p-C(6)H(4)(COO)(2)].H(2)O (6), [Ag(4)]ClO(4) (7), [Cu(4)(2)(H(2)O)(2)](CH(3)COO)(2).2H(2)O (8), [Zn(4)(2)(H(2)O)(2)](NO(3))(2) (9), [Ni(4)(2)(N(3))(2)].2H(2)O (10), and [Ag(5)]ClO(4) (11). All the structures were established by single-crystal X-ray diffraction analysis. Crystal data for 6: monoclinic, C2/c, a = 23.766(3) A, b = 12.0475(10) A, c = 13.5160(13) A, beta = 117.827(3) degrees, Z = 4. For compound 7: orthorhombic, P2(1)2(1)2(1), a = 7.2495(4) A, b = 12.0763(7) A, c = 19.2196(13) A, Z = 4. For compound 8: monoclinic, P2(1)/n, a = 8.2969(5) A, b = 12.2834(5) A, c = 17.4667(12) A, beta = 96.5740(10) degrees, Z = 2. For compound 9: monoclinic, P2(1)/n, a =10.5699(3) A, b = 11.5037(3) A, c = 13.5194(4) A, beta = 110.2779(10) degrees, Z = 2. For compound 10: monoclinic, P2(1)/n, a = 9.8033(3) A, b = 12.1369(5) A, c = 13.5215(5) A, beta = 107.3280(10) degrees, Z = 2. For compound 11: monoclinic C2/c, a = 18.947(2) A, b = 9.7593(10) A, c = 19.761(2) A, beta = 97.967(2) degrees, Z = 8. Both complexes 6 and 7 are noninterpenetrating frameworks based on the (6, 3) nets, and 8, 9 and 10 are based on the (4, 4) nets while complex 11 has a twofold parallel interpenetrated network with 4.8(2) topology. It is interesting that, in complexes 6,7, and 11 with three-coordinated planar silver(I) atoms, each ligand 4 or 5 connects three metal atoms, while in the case of complexes 8, 9, and 10 with six-coordinated octahedral metal atoms, each ligand 4 only links two metal atoms, and another imidazole nitrogen atom of 4 did not participate in the coordination with the metal atoms in these complexes. The results show that the nature of organic ligand and geometric needs of metal atoms have great influence on the structure of metal-organic frameworks.     

Synthesis of novel fullerene amino acids and their multifullerene peptides

[60]-Fullerene functionalized amino acids with 4-6 methylene spacers from α-carbon to the nitrogen atom of fulleropyrolidine and corresponding multifullerene peptides have been synthesized.     

Preparation and photochromic properties of oligomeric poly(dimethylsiloxane) with the spiropyran or spirooxazine moiety in the side chain

Spirobenzopyran 1 , with the 3-(diethoxymethylsilyl)-propyl group at the N atom, was synthesized. The condensation reaction of the spiropyran 1 and diethoxydimethylsilane gave oligomeric poly(dimethylsiloxane) with the spiropyran moiety in the side chain. The oligomer was photochromic; its colour changed from colorless to purple-red on uv irradiation and the color faded on visible irradiation or on standing in the dark. The half-decay time of the thermal decoloration was about twice that of monomeric spiropyran dissolved in the dimethylsiloxane oligomer. Photochromic poly(dimethylsiloxane) with the spirooxazine moiety in the side chain was also prepared.     

Synthesis and Crystal Structure of Blue Luminescent Cadmium(II) Coordination Networks with 4,4′-Bis(imidazol-1-ylmethyl)biphenyl from Different Solvent Systems

Two supramolecular complexes, [Cd(bimb)²Cl²] (1) and [Cd(bimb)(DMF)Cl²]·DMF (2) [bimb=4,4′-bis(imidazol-1-ylmethyl)biphenyl], were synthesized by reactions of CdCl²·2.5H²O with bimb ligand in ethanol and N,N′-dimethylformamide (DMF), respectively, and their structures were determined by X-ray crystallography. Complex 1 is an infinite 2D grid network bridged by bimb ligands, and the 2D sheets were further linked by C–H ?Cl hydrogen bonds to form a polycatenated 3D framework. Complex 2 has dicadmium(II) di-μ-chloride units which are connected by bimb bridging ligands to form an infinite non-interpenetrating 2D network. The results provide a nice example of the solvent system exerting a great effect on the construction of supramolecular frameworks.     

On the convergence of finite element solutions to the interface problem for the Stokes system

The Stokes system with a discontinuous coefficient (Stokes interface problem) and its finite element approximations are considered. We firstly show a general error estimate. To derive explicit convergence rates, we introduce some appropriate assumptions on the regularity of exact solutions and on a geometric condition for the triangulation. We mainly deal with the MINI element approximation and then consider P1-iso-P2/P1 element approximation. Results are expected to give an instructive remark in numerical analysis for two-phase flow problems.     

Scale-free statistics of time interval between successive earthquakes

The statistical property of the calm times, i.e., time intervals between successive earthquakes with arbitrary values of magnitude, is studied by analyzing the seismic time series data in California and Japan. It is found that the calm times obey the Zipf–Mandelbrot power law, exhibiting a new scale-free nature of the earthquake phenomenon. Dependence of the exponent of the power-law distribution on threshold for magnitude is examined. As threshold increases, the tail of the distribution tends to become longer, showing difficulty in statistically estimating time intervals of earthquakes.     

The annealing behavior of hydrogen implanted into Al-1.5 at.% Si alloy

We have studied effects of added elements as well as defects on trap-sites of hydrogen in metals. For the purpose, we observed depth profiles and thermal behaviors of hydrogen implanted into Al-1.5 at.% Si alloy samples in an implantation-temperature range of liquid nitrogen temperature (LNT) to 373 K at different doses. The results were compared with those for pure aluminum samples. It was found that hydrogen is trapped as molecules in grain boundaries of Al/Si.     

High-Efficiency ZnCdSe/ZnSSe/ZnMgSSe Green Light-Emitting Diodes

Green light-emitting diodes (LEDs) were fabricated employing a ZnCdSe/ZnSSe triple quantum-well (TQW) active region surrounded by ZnMgSSe cladding layers grown on an n-type (100) GaAs substrate by molecular beam epitaxy (MBE). A 3.5 mW pure green emission was observed for the surface-emitting LED device at a peak wavelength of 513.3 nm (2.415 eV) with a spectral half-width of 11.7 nm (55 meV) under a 20 mA (4.6 V) direct current at room temperature (25°C). These correspond to an external quantum efficiency of 7.2%, a power conversion efficiency of 3.8%, a luminous current efficiency of 66 lm/A, and a luminous efficiency of 14 lm/W.     

Structure and mechanical properties of nylon 6.12 prepared by temperature slope crystallization. I. Crystallization of oriented spherulitic textures

Oriented spherulitic textures of a rod-shaped nylon 6.12 sample were crystallized by the temperature slope method. Crystallization conditions were compared by changing temperatures and growth rates. Three types of textures (negative spherulites, positive spherulites, and spherulitic aggregates) were observed by this method. The negative textures appeared when the growth rate was less than 0.1 mm/h. Crystalline orientation and mechanical properties of the textures were investigated by x-ray diffraction and micro-hardness measurements, respectively. The hydrogen-bonded (010) planes were perpendicular to the growth direction in the negative spherulite, while they were parallel to the growth direction in the positive spherulite. In the spherulitic aggregates, the b axis was parallel to the growth direction, while the (010) planes formed roughly an angle of 45° with the growth direction. Due to the orientation of the hydrogen-boned planes, the negative texture exhibited an anisotropy, with hardness values of 106 MPa and 137 Mpa when measured perpendicular or parallel to the growth direction, respectively.     

Aerobic oxidation of alcohols using bismuth bromide as a catalyst

We developed an environmentally friendly method for aerobic oxidation of alcohols using a commercially available, relatively benign bismuth salt as a catalyst. We found that the catalytic combination of BiBr₃ with nitric acid is key for enhancing the reactivity. The reaction proceeds well under air, making the use of pure oxygen unnecessary. Each of the primary or secondary alcohols tested was oxidized to the corresponding aldehydes or ketones using this protocol.