Organic–Inorganic Hybrid Gold Halide Perovskites: Structural Diversity through Cation Size

Crystal structures of a series of organic–inorganic hybrid gold iodide perovskites, formulated as A₂[Au^II₂][Au^IIII₄] [A=methylammonium (MA) ( 1 ) and formamidinium (FA) ( 2 )], A′₂[I₃]_1−x[Au^II₂]_x[Au^IIII₄] [A′=imidazolium (IMD) ( 3 ), guanidinium (GUA) ( 4 ), dimethylammonium (DMA) ( 5 ), pyridinium (PY) ( 6 ), and piperizinium (PIP) ( 7 )], systematically changed depending on the cation size. In addition, triiodide (I₃⁻) ions were partly incorporated into the AuI₂⁻ sites of 3 – 7 , whereas they were not incorporated into those of 1 and 2 . Such a difference comes from the size of the organic cation. Optical absorption spectra showed characteristic intervalence charge-transfer bands from Au^I to Au^III species, and the optical band gap increased as the size of the cation became larger.     

Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Applying a Mode Selector to Improve the Pulse-Compression Performance of Asymmetric-Coupled-Waveguide-Based Dispersion Compensators

An InGaAsP slab-type asymmetric-coupled-waveguide-based dispersion compensator with a mode selector has been designed and fabricated. The mode selector is necessary to select either a symmetric [with a positive group-velocity dispersion (GVD)] or antisymmetric (with a negative GVD) supermode. These supermodes exist simultaneously in the dispersion-compensation region of the device. Pulse-compression experiments were used to test the dispersion compensator, evaluating the function of the mode selector. A theoretical study of the experimental results shows that the mode selector obtains a very strong selectivity (nearly 100%) for the antisymmetric supermode.     

Circularly polarized light-induced electrogyration in the Au nanoparticles on the ITO

We have found that the gold nanoparticles on the ITO substrates might be considered promising materials for circularly polarized light-induced linear electrogyration (EG). The maximal achieved value of the EG susceptibility described by third-order axial tensor caused by probe circularly polarized light at a wavelength of 1060 nm was equal to about 13 deg/mm at pulsed electric field strength 30.0 V/cm with a duration of about 1 ms. We have revealed that the maximal EG coefficient is achieved for the samples possessing maximal resistivity. The investigated composites possess long-lived EG grating which decreases by not more than 12% after 120 min of laser treatment. Applying a non-circular pump light leads to the diminishing of the observed EG.     

Lithographic design of photosensitive polyarylates based on reaction development patterning

The factors affecting pattern‐forming properties in reaction development patterning were examined with polyarylates with various bisphenol moieties. The developability of the photosensitive polyarylates was dependent on the properties of the subtituent (R) in the bisphenol moieties. The development time decreased in the following order: R?C(CH₃)₂ > fluorenyl unit ? phenolphthalein unit > C(CF₃)₂ > SO₂. This order agreed with that of the reactivity between the polyarylates and ethanolamine, and these orders can be explained by pK_a of the bisphenol used to prepare the polyarylates. The development with NH₂? R′? OH resulted in successful positive‐tone pattern formation. However, pattern formation with the developers containing NH₂? R′? OCH₃ was unsuccessful. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2694–2706, 2006     

Diastereoselective synthesis of new psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type alkene dipeptide isosteres by organocopper reagents and application to conformationally restricted cyclic RGD peptidomimetics

Diastereoselective synthesis of new psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type alkene dipeptide isosteres corresponding to dipeptides having one N-methylamino acid, and application to bioactive peptides, are described. In a key reaction introducing the chiral alpha-alkyl group of the isosteres, organocopper-mediated alkylation of syn-beta-methylated gamma-mesyloxy-alpha,beta-enoate 26a afforded E- and Z-isomers of anti-S(N)2' products in a solvent-dependent manner. The resulting two isosteres, D-Phe-psi[(E)-CH=CMe]-L-Val 27a and D-Phe-psi[(Z)-CH=CMe]-L-Val 28b, which corresponded to trans- and cis-conformers of D-Phe-L-MeVal, respectively, were utilized in a structure-activity relationship study on cyclic RGD peptides 1 and 2, in company with a psi[(E)-CH=CH]-type alkene dipeptide isostere, D-Phe-psi[(E)-CH=CH]-L-Val. The cyclic isostere-containing pseudopeptides 3, 4, and 40 were synthesized and biological activity against integrin alpha(V)beta(3) and alpha(IIb)beta(3) receptors were also evaluated.     

Electrode kinetics of the metal complexes with aminopolycarboxylic acids: Part II. Cadmium-ethylenediamine-N,N,N′,N′-tetraacetate (EDTA) complexes

The d.c. polarographic current-potential curves of Cd(II)-EDTA complexes were examined in the pH range 0.5–10.0, to elucidate the mechanism of their electrode processes and to determine the relevant electrochemical kinetic parameters. It was shown that the first wave observed below pH 3 at ?0.58 to ?0.65 V vs. SCE is the reversible reduction wave of Cd(II) aquo-ion with kinetically-controlled limiting current, and the second wave observed above pH 1.5 at ?0.75 to ?1.21 V vs. SCE corresponds to the simultaneous irreversible reduction of four complex species, CdH₃L⁺, CdH₂L, CdHL^? and CdL^2?, where CdH_pL^(p?2)+ and L^4? denote the protonated complex species with p protons and the unprotonated EDTA ion, respectively. Analysis of the dependence of limiting current on the hydrogen ion concentration led to the conclusion that the preceding reaction determining the behaviour of limiting current is CdH₃L⁺?Cd²⁺+H₃L^? with k₃^d=6.3×10² s^?1 and k₃^f=3.3×10⁶ s^?1M^?1, where k₃^d and k₃^f are the dissociation and formation rate constants, respectively. On the other hand, from analysis of the dependence of half-wave potentials of the second wave on the hydrogen ion concentration, the kinetic parameters of the four complex species were evaluated, and are given in Table 1. Further, it was shown that the cathodic rate constants of these four charge transfer processes at some reference potential together with those of Cd(II)-HEDTA complexes fulfil the linear free energy relationship.