Solid-state luminescence of Au(I) complexes with external stimuli-responsive properties

In the last decade, the field of stimuli-responsive luminescent materials have been intensely emerged because of the high potential application to functional sensors or photoelectronic devices. In particular, luminescent molecular crystals constructed from Au(I) complexes have produced a wide range of examples of luminescent alterations when some external stimulations, such as heat, mechanical stress, vapor (or solvents), were applied to the solid samples. In this review, we describe the recent progress through a summary of the reported Au(I) complexes based on their utilized stimuli-responsive mechanisms, which are categorized in crystal phase transitions (“crystal-to-amorphous”, “crystal-to-crystal” and “single-crystal-to-single-crystal” transitions) and molecular rotation in crystalline media, respectively.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

正电子冲击下氦电离三重微分截面的理论计算

我们发展了一种正电子碰撞原子电离的畸变波Born近似方法， 在这个方法中，正负电子偶素通道通过一个ab initio的光学势附加到入射粒子和靶的相互作用势上，且通道对电离作用被第一次被考虑在正电子碰撞原子电离的过程中. 应用这个方法计算了在50 eV入射能量范围氦的电离的三重微分截面，计算结果和实验数据很好的符合.     

On the Structure of Intermediates in Enyne Gold(I)-Catalyzed Cyclizations: Formation of trans-Fused Bicyclo[5.1.0]octanes as a Case Study

The nature of cyclopropyl gold(I) carbene-type intermediates has been reexamined as part of a mechanistic study on the formation of cis- or trans-fused bicyclo[5.1.0]octanes in a gold(I)-catalyzed cascade reaction. Benchmark of DFT methods together with QTAIM theory and NBO analysis confirms the formation of distinct intermediates with carbenic or carbocationic structures in the cycloisomerizations of enynes.     

On the use of edge cracked short bend beam specimen for PMMA fracture toughness testing under mixed-mode I/II

In this paper an inclined edge cracked short beam specimen subjected to symmetric three-point bend loading was designed and examined for conducting mixed-mode I/II fracture toughness experiments. The aspect ratio (i.e. length to width ratio) and the loading span distance are considered much lower than the other conventional cracked bend beam samples. Crack tip parameters such as stress intensity factors and T-stress were computed numerically for this specimen by several finite element analyses and it was demonstrated that the specimen is able to produce full combinations of mode I and II including pure mode II. The practical capability of the short bend beam specimen was studied experimentally by conducting a set of mixed-mode fracture tests on PolymethylMethacrylate (PMMA) as a well-known model brittle material. The critical stress intensity factors, the direction of fracture kinking and the path of fracture trajectory were investigated both experimentally and theoretically using two stress and strain-based fracture criteria. The fracture toughness of tested PMMA was decreased by moving towards mode II case due to the effect of T-stress on the fracture mechanism of the short bend beam specimen.     

Retracted: A new class of copper(I) complexes with imine-containing chelators which show potent anticancer activity

Seven novel complexes (C₁–C₇) were synthesized by the interaction between Cu(I) metal cation, L₁, L₂, L₃, X and PPh₃, where L₁–L₃ are derivatives of ((pyridine-2-ylmethylene)amino)phenol imine ligands and X = Cl⁻, Br⁻, I⁻, NCS⁻. All the complexes were characterized using infrared, ¹H NMR and ³¹P NMR spectroscopies. The crystal structures of C₁–C₇ were also determined using single-crystal X-ray diffraction. The organization of the crystal structures and the intermolecular interactions are discussed. The supramolecular assemblies are driven by cooperative π…π interactions and hydrogen bonds, followed by CH…π linkages. The potential anticancer effect of C₁–C₇ was assessed for human glioblastoma cells using several anticancer experiments, which showed that these complexes have marked anticancer property against U87 cells. It was also found that the minimum and maximum anticancer effects are shown by C₃- and C₄-treated samples, respectively. Furthermore, theoretical approaches were used to investigate the nature of metal–ligand interactions which suggest a closed-shell and electrostatic character for Cu…N, Cu…P and Cu…X bonds.     

Sustainable synthesis of quinolines (pyridines) catalyzed by a cheap metal Mn(I)-NN complex catalyst

This study represents the first example of a bidentate phosphine-free manganese(I)-NN complex catalyst for the synthesis of quinolines (pyridines) through acceptorless dehydrogenative condensation of various secondary alcohols with amino alcohols. The coupling reactions occurred at 3 mol% catalyst loading and 110°C, and tolerated diverse functional groups. Moderate to excellent yields ranging from 45% to 89% were achieved after 12 hr of reaction. The present protocol provides a concise and environmentally friendly method for the construction of heterocyclic compounds.     

一种考虑界面相物性影响的界面单元法

界面是由复杂的界面相简化而成的,界面破坏实际是界面相材料的破坏。数值计算为了方便,如经典模型和内聚力模型等,都把很薄的界面相作无厚度化处理。导致只能考虑界面的面力,而无法考虑界面相内的应力(平行于界面方向的应力)。使界面失效准则先天性地排除了界面相内部应力的影响,从界面相材料失效机理的角度来看这是不够严谨的。本文将界面相材料等效为一种弹性连续体,由界面本构关系推导得到了一种新的界面单元。该单元具有界面参数易确定、对界面相物性可以进行等效描述等优点。通过商用有限元软件ABAQUS和用户子程序UEL实现了数值分析,并与直接物理模型的数值模拟结果进行对比,证明了本方法的简便及准确性。通过对不同界面相厚度结构的进一步分析,探讨了本文方法的可行范围。     

Ru(II)‐based antineoplastic: A “wingtip” N‐heterocyclic carbene facilitates access to a new class of organometallics that are cytotoxic to common cancer cell lines

The syntheses, structures, and chemotherapeutic activities of Ag(I)‐, Au(I)‐, and Ru(II)‐complexes ligated to a novel N‐heterocyclic carbene ligand, 2‐(4‐nitrophenyl)imidazo[1,5‐a]pyridin‐2‐ylidene ( 1 ), are described. The corresponding complexes, [Ag( 1 )₂][PF₆], [Au( 1 )₂][PF₆] ( 3 ), and [Ru( 1 )(p‐cymene)Cl][PF₆] ( 4 ), were prepared using convenient transmetallation chemistry and characterized using a range of spectroscopic and analytical techniques. X‐ray crystallography revealed that complexes 2 and 3 adopted linear structures whereas 4 exhibited a prototypical “piano‐stool”‐like geometry; the structural assignments were further supported by DFT calculations. A series of in vitro studies revealed that while the aforementioned Ag(I), Au(I) and Ru(II) complexes exhibited significant cytotoxicities against the human colon adenocarcinoma (HCT 116), lung cancer (A549), and breast cancer (MCF7) cell lines, the Ru derivative was most prominent.