Electrical and Optical Properties of Conducting Polymer and Carbons in Nano-Scale Periodic Structure and their Intercalation Effects

Abstract

Nano-scale periodic structures of conducting polymer and carbons, which were prepared by infiltration of polymers and carbons in nano-scale interconnected periodic pores in synthetic opals made of regular array of SiO₂ spheres and then removing SiO₂ by etching, have been found to exhibit novel electrical and optical properties. Their electrical and optical properties in thus fabricated conducting polymer and carbon replicas change drastically upon pyrolysis due to progress of carbonization and graphitization. That is, due to the changes in periodicity, pore size, carbonization degree and crystal structure, electrical conductivity, magnetoconductance and their temperature dependences and optical reflection spectra have changed drastically. These replicas with porous nature can be infiltrated and also intercalated with various materials, resulting in also remarkable changes of properties. The synthetic opal infiltrated with conducting polymer can be electrochemically doped, with which remarkable change of optical properties have been observed due to the shift of the diffraction peak accompanying with the change in refractive index. Alkali metal intercalated carbon and graphite with nano-scale periodic structures have been also studied. The applications of these nano-scale periodic structures of conducting polymer and carbon are also discussed.     

17,17-Dialkyltetrabenzo[a,c,g,i]fluorenes with extremely high solid-state fluorescent quantum yields: relationship between crystal structure and fluorescent properties

Six 17,17-dialkyltetrabenzo[a,c,g,i]fluorenes (dialkylTBFs) 2–7 (methyl to n-hexyl) were prepared by treatment of 17H-tetrabenzo[a,c,g,i]fluorene (TBF) 1 with n-alkyl halides under basic conditions in moderate yields upon column chromatography and recrystallization. All the compounds show intense blue fluorescence in solutions. On the other hand, in the solid state, the fluorescent spectra and the quantum yields (Φ_p) vary with their alkyl chains. In particular, the Φ_p values of 4–7 bearing n-propyl to n-hexyl groups are close to unity, while the fluorescence of 1 is almost quenched. Crystallographic analyses of 2–7 revealed that the TBF moieties have helicene-like chiral structures in the crystals, and that the alkyl groups basically take an all-trans planar conformation. Because the longer alkyl substituents can serve as a spacer to prevent TBF nuclei from aggregation, π–π interactions of the TBF moieties probably play an important role in quenching the solid-state fluorescence. The relationship between the optical properties and molecular arrangements in the crystals are discussed.     

Flexibility Control of Two-Dimensional Coordination Polymers by Crystal Morphology: Water Adsorption and Thermal Expansion

Layer flexibility in two-dimensional coordination polymers (2D-CPs) contributes to several functional materials as it results in anisotropic structural response to external stimuli. Chemical modification is a common technique for modifying layer structures. This study demonstrates that crystal morphology of a cyanide-bridged 2D-CP of type [Mn(salen)]₂[ReN(CN)₄] ( 1 ) consisting of flexible undulating layers significantly impacts the layer configuration and assembly. Nanoplates of 1 showed an in-plane contraction of layers with a longer interlayer distance compared to the micrometer-sized rod-type particles. These effects by crystal morphology on the structure of the 2D-CP impacted the structural flexibility, resulting in dual-functional changes: the enhancement of the sensitivity of structural transformation to water adsorption and modification of anisotropic thermal expansion of 1 . Moreover, the nanoplates incorporated new adsorption sites within the layers, resulting in the uptake of an additional water molecule compared to the micrometer-sized rods.     

Chemical Functionalisation and Photoluminescence of Graphene Quantum Dots

Chemical modification of graphene quantum dots (GQDs) can influence their physical and chemical properties; hence, the investigation of the effect of organic functional groups on GQDs is of importance for developing GQD–organic hybrid materials. Three peripherally functionalised GQDs having a third‐generation dendritic wedge (GQD‐ 2 ), long alkyl chains (GQD‐ 3 ) and a polyhedral oligomeric silsesquioxane group (GQD‐ 4 ) were prepared by the Cu^I‐catalysed Huisgen cycloaddition reaction of GQD‐ 1 with organic azides. Cyclic voltammetry indicated that reduction occurred on the surfaces of GQD‐ 1 – 4 and on the five‐membered imide rings at the periphery, and this suggested that the functional groups distort the periphery by steric interactions between neighbouring functional groups. The HOMO–LUMO bandgaps of GQD‐ 1 – 4 were estimated to be approximately 2 eV, and their low‐lying LUMO levels (<?3.9 eV) were lower than that of phenyl‐C₆₁‐butyric acid methyl ester, an n‐type organic semiconductor. The solubility of GQD‐ 1 – 4 in organic solvents depends on the functional groups present. The functional groups likely cover the surfaces and periphery of the GQDs, and thus increase their affinity for solvent and avoid precipitation. Similar to GQD‐ 2 , both GQD‐ 3 and GQD‐ 4 emitted white light upon excitation at 360 nm. Size‐exclusion chromatography demonstrated that white‐light emission originates from the coexistence of differently sized GQDs that have different photoluminescence emission wavelengths.     

On the Large Time Behavior of Solutions of Hamilton–Jacobi Equations Associated with Nonlinear Boundary Conditions

In this article, we study the large time behavior of solutions of first-order Hamilton–Jacobi Equations set in a bounded domain with nonlinear Neumann boundary conditions, including the case of dynamical boundary conditions. We establish general convergence results for viscosity solutions of these Cauchy–Neumann problems by using two fairly different methods: the first one relies only on partial differential equations methods, which provides results even when the Hamiltonians are not convex, and the second one is an optimal control/dynamical system approach, named the “weak KAM approach”, which requires the convexity of Hamiltonians and gives formulas for asymptotic solutions based on Aubry–Mather sets.     

Synthesis and structural determination of the C33-C42 fragment of symbiodinolide

Symbiodinolide (1) is a polyol macrolide with a molecular weight of 2859 mu. As one of the degradation reactions, cross-metathesis of 2, which is a methyl ester of 1, with ethylene was performed to give the C33-C42 degraded fragment 4. The absolute configuration of 4 was estimated to be (36S,40S) by Mosher method. Stereoselective synthesis of 4 was achieved in 14 steps from l-aspartic acid. Synthetic bis-(S)- and (R)-MTPA esters exhibited the spectroscopic data identical with those of bis-(S)- and (R)-MTPA esters derived from the degraded fragment 4. Thus, the absolute stereochemistry of 4 was elucidated to be (36S,40S).     

Statistical Mechanical Expressions of Slip Length

We provide general derivations of the partial slip boundary condition from microscopic dynamics and linearized fluctuating hydrodynamics. The derivations are based on the assumption of separation of scales between microscopic behavior, such as collision of particles, and macroscopic behavior, such as relaxation of fluid to global equilibrium. These derivations lead to several statistical mechanical expressions of the slip length, which are classified into two types. The expression in the first type is given as a local transport coefficient, which is related to the linear response theory that describes the relaxation process of the fluid. The second type is related to the linear response theory that describes the non-equilibrium steady state and the slip length is given as combination of global transport coefficients, which are dependent on macroscopic lengths such as a system size. Our derivations clarify that the separation of scales must be seriously considered in order to distinguish the expressions belonging to two types. Based on these linear response theories, we organize the relationship among the statistical mechanical expressions of the slip length suggested in previous studies.

     

Pattern classification using optical Mellin transform and circular photodiode array

Scale-invariant pattern classification using a hybrid system combining the optical Mellin transform and a digital signal processing technique is discussed. We accomplish the optical Mellin transform by a logarithmic coordinate transformation using a computer-generated hologram, followed by an optical Fourier transform. Mellin transform patterns are detected with a circular photodiode array, whose output signals are processed by a micro-computer. A new criterion is discussed, in which circular or periodic correlation is employed. Experimental examples are presented.     

Efficient C-H/C-D exchange reaction on the alkyl side chain of aromatic compounds using heterogeneous Pd/C in D2O

[reaction: see text] An efficient and extensive deuterium incorporation using heterogeneous Pd/C-D(2)O-H(2) system into many different types of unactivated C-H bond positions was developed. The present method provides a deuterium gas-free, totally catalytic, and post-synthetic deuterium labeling method in D(2)O media.