Self‐Assembly of Predesigned Trimetallic Macrocycles Based on Benzimidazole as Nonlinear Bridging Motifs: Crystal Structure of a Luminescent Platinum(II) Cyclic Trimer

A trimetallic macrocycle : Starting from nonlinear N‐deprotonated benzimidazole and square‐planar cyclometalated platinum(II ) precursors, cyclic trimers with three metal vertices can be obtained by a general and rational strategy (shown schematically, M=Pt). A complex is formed with 2‐(2‐thienyl)pyridine as chelating ligand which photoluminesces in solution at room temperature.     

Energy‐Level Alignment for Single‐Molecule Conductance of Extended Metal‐Atom Chains

The use of single‐molecule junctions for various functions constitutes a central goal of molecular electronics. The functional features and the efficiency of electron transport are dictated by the degree of energy‐level alignment (ELA), that is, the offset potential between the electrode Fermi level and the frontier molecular orbitals. Examples manifesting ELA are rare owing to experimental challenges and the large energy barriers of typical model compounds. In this work, single‐molecule junctions of organometallic compounds with five metal centers joined in a collinear fashion were analyzed. The single‐molecule i–V scans could be conducted in a reliable manner, and the E_FMO levels were electrochemically accessible. When the electrode Fermi level (E_F) is close to the frontier orbitals (E_FMO) of the bridging molecule, larger conductance was observed. The smaller |E_F?E_FMO| gap was also derived quantitatively, unambiguously confirming the ELA. The mechanism is described in terms of a two‐level model involving co‐tunneling and sequential tunneling processes.     

A Two‐Stage Molecular Retractable Cable Featuring Push‐Button and Rotary Two‐Way Switching Modes

A molecular cage based [2]rotaxane is reported in which the linear thread component can be elongated and contracted in a stepwise manner, mimicking a two‐stage retractable cable that can be operated in both push‐button (free‐selection) and rotary (continuous‐change) modes, depending on the choice of reagents.     

A novel photochromic system of 4,5-dialkenylthiophenes constructed by the smarium diiodide promoted coupling reactions of thiophene-2-carboxylate with aryl ketones

[reaction: see text] The SmI2-promoted coupling reaction of ethyl thiophene-2-carboxylate with aryl ketones (2 equiv), followed by acid-catalyzed dehydration and oxidative aromatization, gave dialkenylthiophenes 1b-d, which underwent electrocyclizations upon irradiation with 300-nm light in CH3CN solution to give the corresponding closed-ring species with absorption lambda(max) approximately 425 nm. The interconversion between dialkenylthiophenes and their corresponding closed-ring species constitutes a novel photochromic system bearing an ester group for potential uses in linkage and wavelength tuning.     

Comparative study of TmI2, SmI2, and SmI2/HMPA in the cross-coupling reactions of 2-acetylthiophene and thiophene-2-carboxylate with carbonyl compounds

The cross-coupling reactions of acetylthiophene or ethyl thiophene-2-carboxylate with aldehydes or ketones were achieved in a regioselective manner by using thulium diiodide in THF solution. Similar coupling reactions were also realized by using samarium diiodide together with excess amounts of hexamethylphosphoramide (HMPA). However, ethyl thiophene-2-carboxylate was inert in SmI₂/THF solution, and acetylthiophene was simply reduced to thienylethanol by SmI₂ in the absence of HMPA.     

海底混响仿真研究

提出了一种新颖的海底混响仿真工程实现模型.它是基于单元散射的理论,通过模拟海底混响形成的物理过程实现仿真,具有仿真效果好,工程上易于实现的特点.根据该模型实现的多通道海底混响模拟器功能强、柔软性好,所产生的海底混响仿真信号无论是在形式上还是在统计特性方面与实测海底混响相比较都有很好的一致性.此外,该模拟器还可以作为目标模拟器或者相控/束控信号源使用.