Chiral monomeric and homochiral dimeric copper(II) complexes of a new chiral ligand, N-(1,2-bis(2-pyridyl)ethyl)pyridine-2-carboxamide: an example of molecular self-recognition

Reaction of Cu(ClO(4))(2) x 6H(2)O with a racemic mixture of the novel chiral ligand N-(1,2-bis(2-pyridyl)ethyl)pyridine-2-carboxamide (PEAH) affords only the homochiral dimeric copper(II) complexes [Cu(2)((R)()PEA)(2)](ClO(4))(2) and [Cu(2)((S)()PEA)(2)](ClO(4))(2) in a 1:1 ratio. The phenomenon of molecular self-recognition is also observed when a racemic mixture of the monomeric copper(II) complex [Cu((R(S))()PEA)(Cl)(H(2)O)] is converted into the homochiral dimeric species [Cu(2)((R(S))()PEA)(2)](ClO(4))(2) via reaction with Ag(+) ion. This is the first report of direct conversion of a racemic mixture of a chiral monomeric copper(II) complex to a mixture of the homochiral dimers.     

Dinuclear copper (II) and nickel (II) systems with planar M2N2O2 bridge

The tridentate ligand systemb (abbreviated as inkR₂) readily yield copper (II) and nickel (II) species of the formula M₂ (inkR₂)₂(CLO₄)₂. 2xH₂O (x=0–1). Dinuclear formulation is based on variable temperature magnetic susceptibility and conductivity data and on the known structure of some related systems. The Cu₂ (inkR₂) ₂ ²⁺ species are strongly antiferromagnetic (?2J=600–800 cm^?1) while the Ni₂(inkR₂) ₂ ²⁺ species are diamagnetic. The major coordination sphere is planar around each metal (II). The metal ions in a dimer are linked by planar M₂N₂O₂ bridge. The copper (II) and nickel (II) species freely form solid solutions. In these statistical scrambling of copper and nickel occur among the metal ion sites of the dimeric structure. Powder epr spectra of such mixed crystals are indicative of axial geometry around copper (II) ion.     

Main‐chain viologen polymers with organic counterions exhibiting thermotropic liquid‐crystalline and fluorescent properties*

A series of viologen polymers with bromide, tosylate, and triflimide as counterions were prepared by either the Menshutkin reaction or metathesis reaction in a common organic solvent. Their polyelectrolyte behavior in methanol was determined by solution viscosity measurements, and their chemical structures were determined by Fourier transform infrared and Fourier transform NMR spectroscopy. They were characterized for their thermotropic liquid‐crystalline properties with a number of experimental techniques. Each of the viologen polymers with organic counterions had a low melting transition or fusion temperature above which it formed either a high‐order smectic phase or a low‐order smectic phase. Each of them also exhibited a smectic‐to‐isotropic transition. The ranges of the liquid‐crystalline phase were 80–88 °C for viologen polymers with tosylate as a counterion and 120–146 °C for viologen polymers with triflimide as a counterion. They had excellent thermal stability. The ranges of thermal stability were 288–329 °C for viologen polymers with tosylate as a counterion and 343–350 °C for viologen polymers with triflimide as a counterion. The fluorescence property for all of the viologen polymers in either aqueous or methanol solution was also included in this study. For example, the viologen polymer containing the 4,4′‐bipyridinium and p‐xylyl units along the backbone of the polymer chain with triflimide as a counterion had an absorption spectrum (λ_max = 265 nm), an excitation spectrum (λ_ex values = 357, 443, and 454 with monitoring at 533 nm), and an emission spectrum (λ_em = 536 nm with excitation at 430 and 450 nm) in methanol. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 659–674, 2002; DOI 10.1002/pola.10134     

Fully aromatic liquid crystalline homopolyesters and copolyesters of 1,1′-binaphthyl-4,4′-diol

A series of fully aromatic, thermotropic polyesters based on 1,1′-binaphthyl-4,4′-diol, BND, was prepared by the melt polycondensation method and characterized for their thermotropic behavior by a variety of experimental techniques. The homopolymer of BND with terephthalic acid formed a nematic melt at 353°C. In contrast, the polyester from BND and 2,6-naphthalenedicarboxylic acid had a melting transition, T_m, above 400°C, so it was not possible with the equipment available to determine whether it formed a nematic melt. All of the copolymers of BND formed nematic melts at much lower T_m values than those of its respective homopolymers, as expected, because of the copolymerization effect of the added monomer. Moreover, all of the copolymers had higher glass transition temperatures, T_g, than those of other liquid crystalline polyesters and higher thermal stabilities. © 1994 John Wiley & Sons, Inc.     

Kinetics and mechanisms of the reactions of thiosulphato-amine complexes of cobalt(III). Part I. Isomerization and base hydrolysis ofcis andtrans isomers of dithiosulphatobis(ethylenediamine) cobalt(III) ion in aqueous solution

Summary Investigations were carried out on the isomerization and base hydrolysis ofcis andtrans forms of dithiosulphatobis-(ethylenediamine)cobalt(III) ions. Thecis form isomerizes to thetrans form in neutral aqueous medium, rates being 1.15, 2.30 and 4.0×10^–5s^–1, respectively at 42, 50 and 58 °C. Thetrans complex isomerizes to thecis form in basic solution only, the rate varying with pH in a sigmoid pattern. In presence of OH^–, an acid-base equilibrium of the complex ion sets in, but only the basic form takes part in the isomerization reaction. Hydrolysis of thecis isomer proceeds through a base-dependent path only, but that of thetrans isomer proceeds both through base-dependent and base-independent paths. The mechanisms are associative in nature. Thetrans form reacts faster thancis in all cases.     

Syntheses, structures, and reactivities of (Fe-NO)6 nitrosyls derived from polypyridine-carboxamide ligands: photoactive NO-donors and reagents for S-nitrosylation of alkyl thiols

Two new iron nitrosyls derived from two designed pentadentate ligands N,N-bis(2-pyridylmethyl)-amine-N'-(2-pyridylmethyl)acetamide and N,N-bis(2-pyridylmethyl)-amine-N'-[1-(2-pyridinyl)ethyl]acetamide (PcPy(3)H and MePcPy(3)H, respectively, where H is the dissociable amide proton) have been structurally characterized. These complexes are similar to a previously reported (Fe-NO)6 complex, [(PaPy(3))Fe(NO)](ClO(4))(2) (1) that releases NO under mild conditions. The present nitrosyls, namely [(PcPy(3))Fe(NO)](ClO(4))(2) (2) and [(MePcPy(3))Fe(NO)](ClO(4))(2) (3), belong to the same (Fe-NO)6 family and exhibit (a) clean (1)H NMR spectra in CD(3)CN indicating S = 0 ground state, (b) almost linear Fe-N-O angles (177.3(5) degrees and 177.6(4) degrees for 2 and 3, respectively), and (c) N-O stretching frequencies (nu(NO)) in the range 1900-1925 cm(-)(1). The binding of NO at the non-heme iron centers of 1-3 is completely reversible and all three nitrosyls rapidly release NO when exposed to light (50 W tungsten bulb). In addition to acting as photoactive NO-donors, these complexes also nitrosylate thiols such as N-acetylpenicillamine, 3-mercaptopropionic acid, and N-acetyl-cysteine-methyl-ester in yields that range from 30 to 90% in the absence of light. The addition of alkyl or aryl thiolate (RS(-)) to the (Fe-NO)6 complexes in the absence of dioxygen results in the reduction of the iron metal center to afford the corresponding (Fe-NO)7 species.     

Enhanced magnetic anisotropy of nickel nanosheet prepared in Na-4 mica

Nanosheets of nickel with thickness equal to 0.6 nm have been grown within the interlayer spaces of Na-4 mica. The sheets are made up of percolative clusters of nanodisks. Magnetization characteristics indicate a superparamagnetic behavior with a blocking temperature of 428 K. The magnetic anisotropy constant as extracted from the coercivity data has been found to be higher than that of bulk nickel by two orders of magnitude. This is ascribed to a large aspect ratio of the nickel nanophase. The Bloch exponent is also found to be considerably different from that of bulk nickel because of a size effect. The Bloch equation is still found to be valid for the two dimensional structures.     

Friedel-Crafts Polymers. 8. Friedel-Crafts Polycondensation of β-Resorcylic Acid or Resorcinol with p-Xylylene Dichloride,p,p′-Dichloromethyldiphenyl Ether,and p,p′-Dichloroacetyldiphenyl Ether

Friedel-Crafts polycondensation of β-resorcylic acid (BRA) with p-xylylene dichloride (PXDC) or 4,4′-dichloromethyldiphenyl ether (DDE) in dioxane could be effected without simultaneous decarboxylation of BRA. The similar polycondensation of BRA with PXDC, DDE, or 4,4′-dichloroacetyldiphenyl ether (DADE) in nitrobenzene or in the absence of solvent at 150°C was associated with decarboxylation of BRA. Polymers having structures isomeric with those of the polycondensation product of BRA formed with subsequent in situ decarboxylation were prepared by Friedel-Crafts polycondensation of resorcinol with the above dichlorides. All the polymer samples were characterized, and those with related structures were compared. The ion-exchange properties of the polymer sample prepared from BRA and DDE in dioxane were studied.     

Synthesis and Characterization of New Polyetheramides

Polyetheramides (PEAs) are prepared by polycondensation of N,N′-diacetyl-o-tolidide with Bisphenol A, C, or F, phenolphthalein, resorcinol, catechol, hydroquinone, or 1,5- or 2,7-dihydroxynaphthalene or ethylene, butylene, propylene, diethylene, or triethylene glycol. The fusible and soluble oligomers are characterized. An attempt is made to bring out the relationship between various properties of PEAs and their structures.