Influence of the "innocent" ligands on the MLCT excited-state behavior of mono(bipyridine)ruthenium(II) complexes: a comparison of X-ray structures and 77 K luminescence properties

The variations in the nonchromophoric ligands of [Ru(L)4bpy]2+ complexes are shown to result in large changes in emission band shapes, even when the emission energies are similar. These changes in band shape are systematically examined by means of the generation of empirical reorganizational energy profiles (emreps) from the observed emission spectra (Xie, P.; et al. J. Phys. Chem. A 2005, 109, 4671), where these profiles provide convenient probes of the differences in distortions from the ground-state structures of the 2,2-bipyridine (bpy) ligands (for distortion modes near 1500 cm(-1)) in the metal-to-ligand charge-transfer (MLCT) excited states for a series of complexes with the same ruthenium(II) bipyridine chromophore. The bpy ligand is nearly planar in the X-ray structures of the complexes with (L)4 = (NH3)4, triethylenetetraamine (trien), and 1,4,7,10-tetraazacyclododecane ([12]aneN4). However, for (L)4 = 5,12-rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, the X-ray crystal structure shows that the bpy ligand is twisted in the ground state (a result of methyl/bpy stereochemical repulsion) and the emrep amplitude at about 1500 cm(-1) is significantly larger for this structure than for the complex with (L)4 = 1,4,8,11-tetraazacyclotetradecane, consistent with larger reorganizational energies of the bpy distortion modes in order to form a planar (bpy(-)) moiety in the excited state of the former. The trien and [12]aneN4 complexes have very nearly the same emission energies, yet the 40% smaller vibronic sideband intensity of the latter indicates that the MLCT excited state is significantly less distorted; this smaller distortion and the related shift in the distribution of distortion mode reorganizational energy amplitudes is apparently related to the 36-fold longer lifetime for (L)4 = [12]aneN4 than for (L)4 = trien. For the majority (77%) of the [Ru(L)4bpy]2+ complexes examined, there is a systematic decrease in emrep amplitudes near 1500 cm(-1), consistent with decreasing excited-state distortion, with the excited-state energy as is expected for ground state-excited state configurational mixing in a simple two-state model. However, the complexes with L = [12]aneN4, 1,4,7,10-tetraazacyclododeca-1-ene, and (py)4 all have smaller emrep amplitudes and thus less distorted excited states than related complexes with the same emission energy. The observations are not consistent with simple two-state models and seem to require an additional distortion induced by excited state-excited state configurational mixing in most complexes. Because the stereochemical constraints of the coordinated [12]aneN4 ligand restrict tetragonal distortions around the metal, configurational mixing of the 3MLCT excited state with a triplet ligand-field excited state of Ru(II) could account for some of the variations in excited-state distortion. The large number of vibrational distortion modes and their small vibrational reorganizational energies in these complexes indicate that a very large number of relaxation channels contribute to the variations in 3MLCT lifetimes and that the metal-ligand skeletal modes are likely to contribute to some of these channels.     

Optically transparent Au{111} substrates: flat gold nanoparticle platforms for high-resolution scanning tunneling microscopy

We demonstrate a new type of Au{111} substrate that is both atomically flat and optically transparent, which consists of solution-grown flat gold nanoparticles (FGNPs) deposited on indium tin oxide (ITO)-coated glass. We show that FGNPs are atomically flat single-crystal plates with large {111} faces that expose only 2-4 atomic layers. These FGNPs are excellent platforms for alkanethiol self-assembled monolayers (SAMs) and for high-resolution scanning tunneling microscopy (STM). Our supported FGNPs are also low-cost Au{111} substrates, employing only basic wet chemical techniques in preparation. This approach should be broadly applicable to other types of substrates for scanning probe microscopies.     

The Homoleptic U(NCSe)84– Anion in (Pr4N)4U(NCSe)8·2CFCl3 and Th(NCSe)4(OP(NMe2)3)4·0.5CH3CN·0.5H2O: First Structurally Characterised Actinide Isoselenocyanates

The neutral thorium complex Th(NCSe)₄(OP(NMe₂)₃)₄ and homoleptic octa(isoselenocyanato)uranate anion U(NCSe)₈^4– in (Pr₄N)₄U(NCSe)₈·2CFCl₃ ( 1 ) were synthesised and structurally characterised. (Pr₄N)₄U(NCSe)₈·2CFCl₃ contains the U^IV anion U(NCSe)₈^4– and was characterised using IR spectroscopy and single‐crystal X‐ray diffraction. Th(NCSe)₄(OP(N(CH₃)₂)₃)₄·0.5CH₃CN·0.5H₂O ( 2 ) was characterised using IR and Raman spectroscopy, as well as ³¹P{¹H}, ¹⁵N{¹H}, ¹⁴N{¹H}, ¹³C{¹H}, ¹H and ⁷⁷Se NMR spectroscopy and structurally characterised using single‐crystal X‐ray diffraction. The U(NCSe)₈^4– anion and Th(NCSe)₄(OP(N(CH₃)₂)₃)₄·0.5CH₃CN·0.5H₂O complex are the first structurally characterised actinide‐isoselenocyanates. The crystal structures shows an approximate square antiprismatic arrangement of the ligands around the actinide(IV) atoms.     

The descriptions of new microanatomical structures of the male reproductive system and sperm of Myschocyttarus cassununga (Hymenoptera: Vespidae)

The male reproductive system of Mischocyttarus cassununga consists of two testes, each one with three follicles, as occurs in most Vespidae. The seminal vesicle is divided in two chambers, separated by a constriction, so that the anterior locus is a little larger. In the testicular follicles, the spermatozoa are organized in cysts, with approximately 128 per cyst, where the nuclei are oriented toward the follicle center. The spermatozoa of M. cassununga is about 97 μm in length, which makes them the shortest sperm described for Vespidae. Sperm ultrastructure of M. cassununga is very similar of the others Vespidae. But, despite these similarities, the bilobated mitochondrial derivative represents an autapomorphy for M. cassununga. The subdivision of the seminal vesicle has never been observed in any other Vespidae. Thus, this study supports the validity of insect sperm morphology as a tool for phylogenetic analysis within Hymenoptera.     

Factors Influencing the Outcomes of Collaborative Mathematical Problem Solving: An Introduction

This study is an investigation of the factors that influence the effectiveness of collaboration on open-ended mathematical tasks. Students in Grades 3, 6, and 9 worked in groups of 3 on 2 chance and data tasks-1 related to fair dice and the other related to associations among variables presented on data cards. The groups' outcomes and the types of collaboration observed are investigated in relation to issues raised in the literature. Various phenomena are identified that influence cognitive “lifting,” “hovering,” and “falling,” that is, improvement, no change, and reduction in levels of functioning, respectively. These phenomena include cognitive factors, social or interpersonal factors, and external factors.     

Ink‐Jet Printing,Self‐Assembled Polyelectrolytes,and Electroless Plating: Low Cost Fabrication of Circuits on a Flexible Substrate at Room Temperature

Summary: The driving forces behind the development of flexible electronics are their flexibility, lightweightedness, and potential for low‐cost manufacturing. However, because of physical limitations, traditional thermal processes cause deformations in the flexible substrate. As a result, the adhesion quality of the printed wires is deteriorated. This article reviews recent developments in printing circuits on a flexible substrate by combining self‐assembled polyelectrolytes, ink‐jet printing of a catalyst, and electroless plating of metals. The limitations and potential applications of this technology are also discussed. Experiments implementing this technology demonstrated significant results. By a vibration‐induced assistance during an ink‐jet printing catalyst process, line width and blurring can be controlled to within ±3% variation. Following the IPC 6013 standard for flexible electronics, the results after thermal cycling (288 °C, 6 times) and a hot oil test (260 °C, 3 times) indicated that the metallic circuit had retained excellent adhesion properties and electric characteristics. We also report the first successful demonstration of a metal film in a via‐hole inner wall on a flexible substrate. This novel fabrication method is ideal for the realization of large area, flexible electronics and future multilayer flexible substrate application, such as flexible display, chip on flexible substrate, etc., particularly where traditional lithographic processes can not be applied.

Flexible high‐density circuit on an FR‐4 substrate (left) and picture of via hole with copper inner wall (right).     

Buckling and vibration of rectangular laminates with cut off regions

The pure global buckling and vibration of four sides simply-supported as well as clamped orthotropic rectangular laminates having multiple rectangular cut off regions that are symmetric with respect to mid-plane have been studied by treating the remaining cut off regions as uniform plates with reduced stiffnesses. The variation of stiffness of the plate is represented by Fourier series. Some numerical results for the pure global buckling bad prediction due to its reduced flexural stiffness for typical cases of rectangular middle-plane symmetric cut off regions are presented.     

Studying Spatial Distributions of Influenza Hemagglutinin on the Plasma Membrane of Fibroblasts: A Work in Progress

The major envelope protein of influenza virus, hemagglutinin (HA), mediates the fusion of virus to cell for infection, and can mediate cell-cell fusion. It has been studied as a “raft” protein, as it is found in detergent-resistant membranes (DRM) and trafficks apically in polarized epithelia. Moreover, the viral envelope of influenza itself is rich in sphingomyelin and cholesterol. Using both immunogold electron microscopy and fluorescence resonance energy transfer (FRET) microscopy, we are examining the distribution of HA on the surface of fibroblasts expressing wild-type HA.