Exceptionally Long‐Lived Luminescence Emitted from TbIII Ion Caged in an AgI–TbIII–Thiacalix[4]arene Supramolecular Complex in Water

The compositions and photophysical properties of luminescent ternary complexes of thiacalix[4]arene‐p‐sulfonate (TCAS), Tb^III, and Ag^I ions were determined. At pH 6, Ag^I₂?Tb^III₂?TCAS₂ formed. Moreover, at pH 10, in the presence of a 20‐fold excess of Ag^I and a 50‐fold excess of TCAS with respect to Tb^III, Ag^I₂?Tb^III?TCAS₂ formed as the main luminescent species. The structure of these complexes was proposed: two TCAS ligands are linked by two S–Ag^I–S linkages to adopt a double‐cone supramolecular structure. Furthermore, each Tb^III ion in the former complex accepts O^?, S, O^? donation, whereas in the latter, the Tb^III center accepts eightfold O^? donation. The luminescence quantum yield (Φ) of Ag^I₂?Tb^III₂?TCAS₂ (0.16) was almost equal to that of Tb^III?TCAS, but the luminescence lifetime τ of the former (=1.09 ms) was larger than that of the latter. For Ag^I₂?Tb^III?TCAS₂, the yield Φ (=0.11) was small, which is attributed to the low efficiency of photosensitization (η=0.11). However, the τ value (4.61 ms) was exceptionally large and almost equal to the natural luminescence lifetime of Tb^III (4.7 ms), which is due to the absence of coordinating water molecules (q=0.1). This is compatible with the proposed structure in which the Tb^III ion is shielded by a supramolecular cage that expels coordinated water molecules responsible for luminescence quenching.     

Tandem migration-carboalkoxylation of o-isocyanophenyl acetals leading to benzoxazoles

An efficient approach to benzoxazoles via tandem migration-carboalkoxylation of o-isocyanophenyl acetals has been developed. Both a Lewis acid and base are essential for this reaction, and the BF(3)·OEt(2)/2,4,6-collidine combination is the best choice for cooperative transformation.     

Conformation-controlled luminescent properties of lanthanide clusters containing p-tert-butylsulfonylcalix[4]arene

Dinuclear and cubane-shaped lanthanide cluster complexes containing EuIII)and TbIII were synthesized by step-by-step construction using p-tert-butylsulfonylcalix[4]arene as a cluster-forming ligand. The sulfonylcalixarene adopts a pinched-cone conformation in the dinuclear complexes and a cone conformation in the cubane complexes. Because the calixarene has a large pi-conjugate system expanding over the entire molecule, it behaves as a good antenna chromophore for UV and near-UV light, and a slight conformational change of the calixarene (from cone to pinched-cone and vice versa) has an effect on the energy levels of excited S1 and T1 states. As a result, selectivity is observed in the luminescent properties of dinuclear and cubane-shaped systems of EuIII and TbIII.     

Molecular mobility of interlocked structures exploiting new functions of advanced biomaterials

Cyclic compounds can rotate and/or slide along a polymeric chain in a polyrotaxane structure, and the mobility of the ligands linked by the cyclic compounds is closely related to enhancing the multivalent interaction with binding sites on the receptor proteins. This concept is being exploited in more practical applications in the biomedical and pharmaceutical fields, such as a non-viral gene carriers.     

Permeability retrieval in InP-based waveguide optical device combined with metamaterial

An InP-based Mach-Zehnder interferometer combined with a metamaterial layer consisting of a split-ring resonator array was constructed to measure the complex permeability of the metamaterial. At a wavelength of 1.5 μm, the metamaterial showed non-unity relative permeability induced by magnetic interaction with propagating light in the device. This method of measurement would be useful to determine constitutive parameters in such waveguide-based photonic devices, allowing us to design photonic integrated circuits that make use of metamaterials.     

Fluctuations of expectation values in chaotic systems and broken time-reversal symmetry

Fluctuations of expectation values of observables are calculated in complex quantum systems, such as disordered metallic grains or quantum systems with classical chaotic motion. We derive an exact expression for these fluctuations valid for systems with and without time-reversal symmetry, as well as in the transition region between these two cases. We compare our results with those of a semiclassical theory and with simulations of random matrices.     

逃逸函数算法及其在光学设计中的应用

用阻尼最小二乘法进行光学系统的优化 ,得到的结果往往是评价函数在结构变量空间的一个局部极小值。日本东京工艺大学的一色教授提出了能够跳出此局部极小值继续寻找其它结果的逃逸函数全局优化算法 ,该算法的运行由多个不加或加入逃逸函数的阻尼最小二乘法局部优化组成。描述了逃逸函数的基本原理 ,给出了北京理工大学研制的GOLD软件在加入了这种算法后对光学系统进行全局优化的设计实例。实验证明了逃逸函数算法是提高光学设计效率和质量的一种有效工具。     

Intense THz-radiation from semiconductors under magnetic field irradiated with femtosecond laser pulses

The THz-radiation power from InAs reaches sub-mW level in a 1.7-T magnetic field irradiated with femtosecond laser pulses of 1.5-W average power. The THz-radiation power is related almost quadratically both to the magnetic field and to the excitation laser power. Furthermore, the THz-radiation spectrum is found to be controlled by the excitation pulsewidth, chirp direction of the excitation pulse, and the magnetic field.     

Growth and annealing effect of high-quality ZnSe:N/ZnSe by MOCVD

The ZnSe : N epitaxial layers were grown on (1 1 0) ZnSe substrates in a low-pressure metalorganic chemical vapor deposition (MOCVD) system using hydrogen as a carrier gas, and using ammonia as a dopant source. In order to obtain highly doped ZnSe : N epitaxial layers, the optimum growth and doping conditions were determined by studying the photoluminescence (PL) spectra from the ZnSe epitaxial layers grown at different ammonia flux and VI/II flux ratio. Furthermore, in order to enhance the concentration of active nitrogen in ZnSe epitaxial layer, a rapid thermal anneal technique was used for post-heat-treating. The results show that the annealing temperature of over 1023 K is necessary. Beside, a novel treatment method to obtain a smooth substrate surface for growing high quality ZnSe epitaxial layers is also described.