Built to order: molecular tinkertoys from the [Re(6)(mu(3)-Se)(8)](2+) clusters

Ligand substitution of [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(CH(3)CN)](SbF(6))(2) (1) with pyridyl-based ligands, 2,4,6-tri-4-pyridyl-1,3,5-triazine (L1) and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (L2), produced respectively the star-shaped tricluster (T1) and tetracluster (T2) arrays, wherein three (T1) and four (T2) units of the [Re(6)(mu(3)-Se)(8)](2+) core-containing clusters are interconnected by the corresponding bridging ligands. These novel supramolecular assemblies were characterized by a combination of NMR ((1)H and (31)P) spectroscopy, ESI-MS, and microanalysis. The molecular and solid-state structures of T1 have also been established by single-crystal X-ray diffraction.     

Synthesis, structure, and fluorescence of the novel cadmium(II)-trimesate coordination polymers with different coordination architectures

Three novel complexes, Cd3tma2*13H2O (1), Cd3tma2*dabco*2H2O (2), and Cd3Htma3*8H2O (3) (tma = trimesate), of cadmium(II)-trimesate coordination polymers are obtained from hydrothermal reaction. 1 (C18H32O25Cd3) crystallizes in the monoclinic C2/c space group [a = 18.985(2) A, b = 7.3872(6) A, c = 20.432(2) A, = 97.1660(10), and Z = 4]. 2 (C24H22N2O14Cd3) crystallizes in the monoclinic P2(1)/c space group [a = 10.1323(2) A, b = 19.5669(5) A, c = 13.15880(10) A, = 108.9810(10), and Z = 4]. 3 (C27H28O26Cd3) belongs to the trigonal P31c space group [a = 15.7547(3) A, b = 15.7547(3) A, c = 7.93160(10) A, and Z = 2]. The Cd(II) centers in the three complexes are bridged by tma ligands in the coordination fashion of unidentate, bridging unidentate, bidentate, chelating bis-bidentate, chelating/bridging bis-bidentate, or chelating/bridging bidentate to form the T-shaped molecular bilayer motif for 1, chicken-wire-like motif for 2, and honeycomb-like porous structure for 3, respectively, in which the T-shaped molecular bilayer motif and chicken-wire-like motif are further interlinked in interdigitating or alternating fashion to construct the different coordination architectures. These three complexes exhibit strong fluorescent emission bands at 355 nm (lambda(ex) = 220 nm) for 1, 437 nm (lambda(ex) = 365 nm) for 2, and 353 nm (lambda(ex) = 218 nm) for 3 in the solid state at room temperature.     

Syntheses and structures of six compounds in the A2LiMS4 (A=K, Rb, Cs; M=V, Nb, Ta) family

Six new compounds in the A₂LiMS₄ (A=K, Rb, Cs; M=V, Nb, Ta) family, namely K₂LiVS₄, Rb₂LiVS₄, Cs₂LiVS₄, Rb₂LiNbS₄, Cs₂LiNbS₄, and Rb₂LiTaS₄, have been synthesized by the reactions of the elements in Li₂S/S/A₂S₃ (A=K, Rb, Cs) fluxes at 773 K. The A and M atoms play a role in the coordination environment of the Li atoms, leading to different crystal structures. Coordination numbers of Li atoms are five in K₂LiVS₄, four in A₂LiVS₄ (A=Rb, Cs) and Cs₂LiNbS₄, and both four and five in Rb₂LiMS₄ (M=Nb, Ta). The A₂LiVS₄ (A=Rb, Cs) structure comprises one-dimensional chains of tetrahedra. The Rb₂LiMS₄ (M=Nb, Ta) structure is composed of two-dimensional layers. The Cs₂LiNbS₄ structure contains one-dimensional chains that are related to the Rb₂LiMS₄ layers. The K₂LiVS₄ structure contains a different kind of layer.     

Self-assembled,wormlike-cylinder network of polystyrene-block-poly(ethylene oxide) micelles in solution

We report the formation of a highly entangled and interconnected, self-assembled, wormlike-cylinder network of polystyrene-block-poly(ethylene oxide) in N, N-dimethylformamide/water. In this system, N,N-dimethylformamide was a common solvent and water was a selective solvent for the poly(ethylene oxide) blocks. The degrees of polymerization of the polystyrene and poly(ethylene oxide) blocks were 962 and 227, respectively. The network was formed at copolymer concentrations higher than 0.4 wt % and consisted of self-assembled, wormlike cylinders that were interconnected by Y-shaped, T-shaped, and multiple junctions. The network morphology was visualized with transmission electron microscopy. Capillary viscometry measurements revealed an order-of-magnitude increase in the inherent viscosity of the colloidal system upon the formation of the network. A similar effort to obtain a wormlike-cylinder network in an N,N-dimethylformamide/acetonitrile system, in which acetonitrile was a selective solvent for the poly(ethylene oxide) blocks, was unsuccessful even at high copolymer concentrations; instead, the wormlike cylinders showed a tendency to align. The viscosity measurements also did not show a substantial increase in the inherent viscosity. Thus, the solvent played a critical role in determining the formation of the self-assembled, wormlike-cylinder network. This formation of the network resulted from an interplay between the end-capping energy, bending energy (curvature), and configurational entropy of the self-assembled, wormlike-cylinder micelles that minimized the free energy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3605–3611, 2006     

Resonant coupling of bound excitons with LO phonons in ZnO: excitonic polaron states and Fano interference

We report on a photoluminescence observation of robust excitonic polarons due to resonant coupling of exciton and longitudinal optical (LO) phonon as well as Fano-type interference in high quality ZnO crystal. At low enough temperatures, resonant coupling of excitons and LO phonons leads to not only traditional Stokes lines (SLs) but also up to second-order anti-Stokes lines (ASLs) besides the zero-phonon line (ZPL). The SLs and ASLs are found to be not mirror symmetric with respect to the ZPL, strongly suggesting that they are from different coupling states of exciton and phonons. Besides these spectral features showing the quasiparticle properties of exciton-phonon coupling system, the first-order SL is found to exhibit characteristic Fano lineshape, caused by quantum interference between the LO components of excitonic polarons and the continuous phonon bath. These findings lead to a new insight into fundamental effects of exciton-phonon interactions.     

Effect of chemical potential on the computer simulation of hydrogen storage in single walled carbon nanotubes

Hydrogen is a kind of clean, sustainable and renewable energy carrier. Of the problems to be solved for the utilization of hydrogen energy, how to store and transport hydrogen has been given high priority on the research agenda. Recently, carbon nanotubes (CNTs) were reported to be very promising candidates for hydrogen uptake[1], which may have possibility to satisfy the benchmark set by the US Department of Energy (DOE) Hydrogen Plan for fuel cell powered vehicles: a gravimetric density …     

多孔二氧化硅中Gd3+ → Eu3+的能量传递

通过水热反应法，获得了单掺和双掺Eu³⁺，Gd³⁺的多孔二氧化硅组装体，研究了掺杂体系的光谱特性，观察到Gd³⁺ → Eu³⁺的能量传递。分析了能量传递过程，探讨了在多孔二氧化硅中Gd³⁺→Eu³⁺的能量传递的机理，其机理主要为电偶极-电偶极相互作用。     

Itosides A – I,New Phenolic Glycosides from Itoa orientalis

Eight new benzoylated gentisyl alcohol (=2‐(hydroxymethyl)benzene‐1,4‐diol) glucosides, itosides A–H ( 1 – 8 ), together with the new pyrocatechol (=benzene‐1,2‐diol) glycoside itoside I ( 9 ) were isolated from the bark and twigs of Itoa orientalis (Flacourtiaceae). In itosides B–D ( 2 – 4 ), the gentisyl alcohol moiety was esterified by 1‐hydroxy‐6‐oxocyclohex‐2‐ene‐1‐carboxylic acid, while itosides E–H ( 5 – 8 ) contained instead an additional 2‐hydroxybenzoic acid moiety. The compounds were accompanied by the known derivatives 4‐hydroxytremulacin ( 10 ), poliothyrsoside ( 11 ), poliothyrsin ( 12 ), homaloside D ( 13 ), tremulacin, and pyrocatechol β‐D ‐glucopyranoside. The structures of the new compounds were elucidated by spectral and chemical methods.