High‐Nuclear Organometallic Copper(I)–Alkynide Clusters: Thermochromic Near‐Infrared Luminescence and Solution Stability

Cu(CF₃COO)₂ reacts with tert‐butylacetylene (tBuC≡CH) in methanol in the presence of metallic copper powder to give two air‐stable clusters, [Cu^I₁₅(tBuC≡C)₁₀(CF₃COO)₅]?tBuC≡CH ( 1 ) and [Cu^I₁₆(tBuC≡C)₁₂(CF₃COO)₄(CH₃OH)₂] ( 2 ). The assembly process involves in situ comproportionation reaction between Cu²⁺ and Cu⁰ and the formation of two different clusters is controlled by reactants concentration. The clusters consist of Cu₁₅ and Cu₁₆ cores co‐stabilized by strong by σ‐ and π‐bonded tert‐butylethynide and CF₃COO^? (together with methanol molecule in 2 ). Their stabilities in solution were confirmed using electrospray ionization mass spectrometry in which the cluster core remains intact for 1 in chloroform and acetone, and for 2 in acetonitrile. Strong thermochromic luminescence in the near infrared (NIR) region was observed in the solid‐state. Of particular interest, the emission maximum of 1 is red‐shifted from 710 nm at 298 K to 793 nm at 93 K, along with a 17‐fold fluorescence enhancement. In contrast, 2 exhibits red shift from 298 to 123 K followed by blue shift from 123 to 93 K. The emission wavelength was correlated with the structural parameters using variable‐temperature X‐ray single‐crystal analyses. The rich cuprophilic interaction plays a significant role in the formation of ³LMCT (tBuC≡C→Cu_x) excited state mixed with cluster‐centered (³CC) characters, which can be considerably influenced by temperature, leading to thermochromic luminescence. The present work provides 1) a new synthetic protocol for the high‐nuclear Cu^I–alkynyl clusters; 2) a comprehensive insight into the mechanism of thermochromic luminescence; 3) unusual emissive materials with the characters of NIR and thermochromic luminescence simultaneously.     

Perfect impedance-matched left-handed behavior in combined metamaterial

Matching the impedance of a medium to free space, which is usually not available in natural materials, is an important advance in metamaterials. In this paper, we present a simple mechanism for a perfect impedance-matched left-handed metamaterials, that reveals a nearly zero reflection over operating frequency. This finding is based on the independent manipulation of the electric response without any effect on the magnetic one.     

Regular conjugated terpolymers comprising two different acceptors and bithiophene donor in repeating group: Effect of strong and weak acceptors on semiconducting properties

Diketopyrrolopyrrole (DPP)‐based terpolymers—P(DPP‐TPyT) and P(DPP‐T3MTT)—bearing bithiophene donating groups and weak accepting units such as pyridine (Py) or methyl thiophene‐3‐carboxylate (3MT), in the polymer backbone, were successfully synthesized. Although the two polymers had similar physical and electrochemical properties, grazing incidence X‐ray diffraction patterns of P(DPP‐TPyT) and P(DPP‐T3MTT) showed mixed and edge‐on orientations, respectively, in thermally annealed films. Accordingly, the P(DPP‐T3MTT) showed twice the hole mobility of P(DPP‐TPyT) in a thin‐film transistor, and a blended film of P(DPP‐T3MTT) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₁BM) showed better power conversion efficiency in a polymer solar cell. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1339‐1347     

Triple negative permeability band in plasmon-hybridized cut-wire-pair metamaterials

We expand the picture of plasmon hybridization in metamagnetic structure via numerically studying the electromagnetic coupling in the metallic cut-wire-pair super cells. It is shown that a triple negative permeability band can be achieved by systematically controlling the plasmon hybridization in such the structure. The corresponding transmission properties as well as the electromagnetic responses of the plasmon-hybridized structures were presented by using the finite integration technique simulations. Our results would reveal a promising design to obtain the multiple negative refractions based on the combination of hybridized cut-wire-pairs and continuous wires.     

Long-lived emission from platinum(II) terpyridyl acetylide complexes

Photoluminescence with high quantum yield and long lifetime from a triplet metal-to-ligand charge transfer (MLCT) excited state in fluid solution at room temperature has been observed for a series of platinum(II) 4'-p-tolyl-terpyridyl acetylide complexes.     

Controlled photocyclization, photodimerization, and photoisomerization of stilbazole salts within Nafion membranes

[reaction: see text] Water- and methanol-swollen Nafion membranes were used as microreactors to successfully control the photochemical reaction pathway of stilbazole derivatives. Of particular interest is the production of azaphenanthrene (the product not obtainable in homogeneous solution) in high yield under high bulk concentration.     

Numerical analysis of a moving boundary problem in coastal hydrodynamics

A finite element model to tackle the moving boundary problem of wave run-up on moderately steep slopes is developed. The special aspects considered in this study are (1) the modification of shallow water equations to accommodate the effect of vertical accelerations and (2) the use of Lagrangian acceleration coupled with an element that adapts itself to the moving boundary closely. The pressure term in the one-dimensional momentum equation is derived using the Eulerian equation in the vertical direction. This takes care of the vertical accelerations which are significant during the motion of a wave on moderately steep slopes. The element near the boundary is allowed to change its dimension so that the fluid boundary is closely followed. Such a flexible element precludes the need for approximation of the variables with regard to the indefinite position of the boundary. This element is split into two when its dimension becomes unduly large compared to the unchanging elements. The need for such a splitting is shown by an examination of the entries in the global matrix. Results of water profile as a wave runs up a structure are given. A brief history of the work on similar problems is outlined.     

Optimal design of loudspeaker arrays for robust cross-talk cancellation using the Taguchi method and the genetic algorithm

An optimal design technique of loudspeaker arrays for cross-talk cancellation with application in three-dimensional audio is presented. An array focusing scheme is presented on the basis of the inverse propagation that relates the transducers to a set of chosen control points. Tikhonov regularization is employed in designing the inverse cancellation filters. An extensive analysis is conducted to explore the cancellation performance and robustness issues. To best compromise the performance and robustness of the cross-talk cancellation system, optimal configurations are obtained with the aid of the Taguchi method and the genetic algorithm (GA). The proposed systems are further justified by physical as well as subjective experiments. The results reveal that large number of loudspeakers, closely spaced configuration, and optimal control point design all contribute to the robustness of cross-talk cancellation systems (CCS) against head misalignment.     

A luminescent chemosensor with specific response for Mg2+

A novel chemosensor, a cyclometalated platinum(II) bipyridyl acetylide complex containing a monoazacrown moiety in the acetylide ligand, which can signal Mg(2+) specifically and display large changes both in color and in luminescence intensity upon complexation with Mg(2+), is described.