Chiral molecular glass: synthesis and characterization of enantiomerically pure thiophene-based [7]helicene

Synthesis of thiophene-based [7]helicenes, which are functionalized for both design of organic chiral glasses with strong chiroptical properties and for further homologation to higher [n]helicenes, is reported. The key synthetic transformations are kinetic resolution of the intermediate diketone and the annelation step forming the center benzene ring by means of an intramolecular McMurry reaction. Based upon X-ray crystallographic determinations of the absolute configurations for (+)-enantiomers of the diketone and the [7]helicene, stereochemical correlation between the (R) axial chirality of the diketone and the (M) helical chirality of the [7]helicene is established. One such enantiopure trimethylsilyl-substituted [7]helicene possesses enchanced chiroptical properties and forms a chiral molecular glass.     

The synthesis of 6-C-substituted 9-methoxymethylpurine derivatives

6-Cyanomethylene ( 2 ), which was prepared via 1 by substitution with malononitrile, has been catalytically hydrogenated to the α-(aminomethylene)-9-(methoxymethyl)-9H-purine-6-acetonitrile ( 3 ) in good yield using N,N-dimethylformamide-benzene as solvent over Pd-C under medium pressure. Intermediate 3 was derived to aldehyde 5 by hydrolysis with acid or base. Substitution of 3 with amines gave the corresponding alkylamines 6 and 7 . Reaction of 3 with hydrazine and acetamidine hydrochloride gave pyrazole derivative 8 and pyrimidine derivative 9 , respectively.     

Double percolation effect on the electrical conductivity of conductive particles filled polymer blends

Electrical conductivity of carbon black (CB) filled polymer blends which are incompatible with each other was studied as a function of the polymer's blend ratio. Transmission electron microscope (TEM) analysis shows that CB distributes unevenly in each component of a polymer blend. TEM photographs of phase structure of solvent extracted HDPE/PMMA blend and solvent extraction experiments of PMMA/PP blend detect the blend ratio at which the structural continuity of filler rich phase is formed. The electrical conductivity of polymer blends is found to be determined by two factors. One is the concentration of CB in the filler rich phase and the other is the structural continuity of this phase. This double percolation affects the conductivity of conductive particle filled polymer blends.     

Effect of polymer on electron-donating character of polymer donor. II. Formation of charge-transfer complex between polymers containing N-dimethylaniline group and trinitrotoluene

Formation of charge-transfer complexes with trinitrotoluene (TNT) as a common acceptor was studied in detail by using dimethyltoluidine (DMT), poly-N-dimethyl-p-aminostyrene (poly-ASt), and also copolymers of aminostyrene (ASt) and styrene (St) as donors. A smooth bathochromic shift in λ_max was observed with increasing ASt unit content in copolymers. Values of the constant for charge transfer complex formation K_CT were found to increase smoothly with ASt unit content. However, the K_CT value with DMT did not coincide with the value extrapolated from the plot of K_CT value versus ASt unit content to zero ASt unit content, but was found to be much higher than the limiting value, in contradiction to the results obtained with maleic anhydride (MAnh). The entropy of complex formation with DMT was found to be exceptionally small; this small value may be responsible for the high K_CT value with DMT.     

A lithiation approach to cordycepin analogues variously substituted at the C-8 position

Several 8-substituted cordycepins were prepared via LDA lithiation of 2′,5′-bis-O-(t-butyldimethylsilyl)-cordycepin and successive reactions of its C-8 lithiated species with various types of electrophiles. Wittig reaction of the 8-formyl derivative was also examined.     

Heterometallic hexanuclear cluster with an S = 8 spin ground state: MnII[MnII(hfac)2]3[NiII(pao)3]2 (hfac- = hexafluoroacetylacetonate,pao- = pyridine-2-aldoximate)

The heterometallic Mn(II)(4)Ni(II)(2) title compound has been synthesized and characterized by X-ray crystallography. The compound consists of a Ni-Mn-Ni linear moiety, [[Ni-(mu-NO)(3)](2)-Mn], linked by oximate bridges and three Mn(II) hfac terminal units attached by oximate oxygens in a di-mu-oxo fashion, forming a novel heterometallic cluster: Mn[Mn(hfac)(2)](3)[Ni(pao)(3)](2) (1). Magnetic measurements reveal the antiferromagnetic nature of the oximate pathway between Mn(II) and Ni(II) metal ions, which imposes an unusual high-spin ground state (S = 8) for 1.