Stereoselective Thermal Conversion of s-trans-Diallene into Dimethylenecyclobutene via s-cis-Diallene in the Crystalline State

A conrotatory [2+2] cyclization is the second step in the solid-state thermal reaction of s-trans-tetraaryldibromohexatetraenes 1 to cyclobutenes 4 . Prior to the cyclization 1 rearranges into the cis conformer 3 . Surprisingly the thermal rearrangement and the stereoselective cyclization occur readily in spite of the required motion of the sterically bulky substituents. R=Ph, p-MeC₆H₄.     

Acid-catalyzed copolymerization of aspartic acid with ω-amino acid. -Biodegradability and Ca2+ chelating ability of poly(aspartic acid -Co- ω-amino acid)-

The polycondensation of L-aspartic acid (1) with various ω-amino acids (2) using phosphoric acid catalyst produced poly(succinimide-co-ω-amino acid)s (3), which was followed by alkali hydrolysis to poly(aspartic acid-co-ω-amino acid) (4). The Ca²⁺ chelating abilities of 4 depended on the content of comonomer unit in the copolymer and on the kind of amino acids. For the copolymer using 11-aminoundecanoic acid (2d) as a comonomer, the Ca²⁺ chelating ability was higher than that of poly(sodium acrylate). For poly(aspartic acid-co-6-aminocaproic acid) (4c), there was a tendency to increase according to the increase of 6-aminocaproic acid (2c) unit in the copolymer. The biodegradability of the copolymer in the case of 2c as a comonomer, evaluated by TOC measurement, was 63%, which was the highest degradability among the copolymers having different methylen length. The biodegradability of 4c decreased with increasing the 2c unit in 4c.     

[(1R,2R)‐1,2‐Di­amino­cyclo­hexane‐κ2N,N′](α‐di­imine‐κ2N,N′)­platinum(II) bis­(hexa­fluoro­phosphate), where α‐di­imine is 2,2′‐bi­pyridine and 1,10‐phen­anthroline

The title Pt^II complexes, viz. (2,2′‐bi­pyridine‐κ²N,N′)[(1R,2R)‐1,2‐di­amino­cyclo­hexane‐κ²N,N′]­platinum(II) bis­(hexa­fluoro­phosphate), [Pt(C₆H₁₄N₂)(C₁₀H₈N₂)](PF₆)₂, and [(1R,2R)‐1,2‐di­amino­cyclo­hexane‐κ²N,N′](1,10‐phenanthroline‐κ²N,N′)platinum(II) bis­(hexa­fluoro­phosphate), [Pt(C₆H₁₄N₂)(C₁₂H₈N₂)](PF₆)₂, containing an aromatic α‐di­imine and a non‐planar di­amino­cyclo­hexane, both form a ladder‐type structure, which is constructed via loose π–π stacking on the α‐di­imine ligands and hydrogen bonding between the cyclic amines and the counter‐anions. In the former compound, there are two independent complex cations, both of which have a twofold axis through the Pt atom.     

Dichloro(4,4′‐dinonyl‐2,2′‐bipyridine‐κ2N,N′)platinum(II)

The title compound, [PtCl₂(C₂₈H₄₄N₂)], is a new square‐planar Pt^II complex con­taining a bi­pyridine moiety with two long alkyl‐chain substituents. The complex forms a segregated packing structure made up of the alkyl‐chain layers and paired coordination sites.     

Target Residues from the Interaction of Copper with 40MeV/u 40Ar Ions

Cross Sections and average forward recoil range FW were measured for target residues from the interaction of Cu with 40MeV/u ⁴⁰Ar ions using off-line y-ray spectroscopy.The mass yield distribution was obtained with assumption of charge distribution.The linear momentum transfer was calculated from FW values.A comparison with similar results of ¹²C+Cu and ²⁰Ne+Cu reactions indicates that the fractional linear momentum transfer,corresponding to central collisions,decreases with increasing projectile mass at the same energy per nucleon. However,the excitation energy of the composite system created from the collisions of Cu with ⁴⁰Ar ions reached the value of 5.3MeV /u and was higher than those from the collisions with ¹²C and ²⁰Ne ions.     

Phosphorescence at Low Temperature by External Heavy-Atom Effect in Zinc(II) Clusters

Luminescent Zn^II clusters [Zn₄L₄(μ₃-OMe)₂X₂] (X=SCN ( 1 ), Cl ( 2 ), Br ( 3 )) and [Zn₇L₆(μ₃-OMe)₂(μ₃-OH)₄]Y₂ (Y=I⁻ ( 4 ), ClO₄⁻ ( 5 )), HL=methyl-3-methoxysalicylate, exhibiting blue fluorescence at room temperature (λ_max=416≈429 nm, Φ_em=0.09–0.36) have been synthesised and investigated in detail. In one case the external heavy-atom effect (EHE) arising the presence of iodide counter anions yielded phosphorescence with a long emission lifetime (λ_max=520 nm, τ=95.3 ms) at 77 K. Single-crystal X-ray structural analysis and time-dependent density-functional theory (TD-DFT) calculations revealed that their emission origin was attributed to the fluorescence from the singlet ligand-centred (¹LC) excited state, and the phosphorescence observed in 4 was caused by the EHE of counter anions having strong CH−I interactions.     

Rational Molecular Design and Synthesis of Highly Thermo‐ and Photostable Near‐Infrared‐Absorbing Heptamethine Cyanine Dyes with the Use of Fluorine Atoms

Highly thermo‐ and photostable, near‐infrared‐absorbing heptamethine cyanine dyes were achieved with the use of fluorine‐containing components. In particular, one prepared heptamethine cyanine dye, bearing a tetrakis(pentafluorophenyl)borate as a counter anion and an N‐ethyl‐2,2,2‐trifluoroacetamido group at the meso position, showed not only a high decomposition temperature (T_dt), but also very high photostability toward white LED irradiation.     

Synthesis of macrocyclic heteroarylenes by consecutive inter- and intramolecular cycloadditions of thiophenylene-tethered triynes

Consecutive inter- and intramolecular [2+2+2] cycloadditions of various thiophenylene-tethered triynes were comprehensively studied by using chiral Rh catalysts. When we started from 2,3- and 3,4-thiophenylene-tethered substrates, dimerization proceeded and chiral tetraheteroarylenes were obtained. In contrast, reactions of 2,5-thiophenylene-tethered substrates gave hexaheteroarylenes as trimers. When bis- and tris(2,5-thiophenylene)-tethered triynes were used, mixtures of dimers and trimers were obtained, which included macrocyclic systems that contained up to 12 aromatic rings, and their photophysical properties were measured.     

Palladium-catalyzed C3-selective mono-arylation of 4-hydroxycoumarin

4-Hydroxycoumarin (1) is a useful synthon in synthetic organic chemistry and a basic skeleton of several bioactive compounds. The direct functionalization of 1 with novel catalytic system would provide an efficient meaning for construction of a chemical library. Here, we developed a new catalytic system using palladium(II) acetate for the C3 regioselective mono-arylation of 1. The 3-mono-arylated and the 3,4-disubstituted coumarins were synthesized to enable derivatization. This palladium-catalyzed direct arylation of 1 is effective for rapid diversification and chemical library construction.