The nano-scale molecule with the longest delocalized metal-metal bonds: linear heptacobalt(II) metal string complexes [Co7(micro7-L)4X2

A new type of pyrazine-modulated oligo-alpha-pyridylamino ligands, N2-(pyrazin-2-yl)-N6-(6-(pyrazin-2-ylamino)pyridin-2-yl)pyridine-2,6-diamine (H3pzpz) and N2-(pyrazin-2-yl)-N6-(6-(pyridin-2-ylamino)pyridin-2-yl)pyridine-2,6-diamine (H3tpz), were synthesized and characterized by IR, 1H NMR and MS(FAB). Using and , the linear heptacobalt(II) metal string complexes [Co7(micro7-L)4X2] (L=pzpz3-, X=Cl-, NCS-; L=tpz3-, X=Cl-, X=NCS-) were synthesized and structurally characterized. The structures showed the shortest Co-Co distance (2.194 A) and the longest Co chain (13.5 A) obtained to date with direct Co-Co bonds. The Co-Co distances are in the range 2.194-2.309 A. Electrochemical studies showed two reversible oxidations and one reversible reduction, while all the redox reactions of H3pzpz complexes, and , occurred at higher potentials than H3tpz complexes, and . The complexes are fairly stable to oxidation. Temperature-dependent magnetic research on revealed anomalous magnetic behavior with intermediate magnetic moment values between quartet and doublet states, and deviation from the Curie-Weiss law.     

New versatile ligand family, pyrazine-modulated oligo-alpha-pyridylamino ligands, from coordination polymer to extended metal atom chains

Here we designed and synthesized a new ligand, di(2-pyrazyl)amine (Hdpza) (1) and studied its coordination modes and the corresponding complexes with Cu(II), Co(II), Ni(II) and Cr(II). Hdpza is an analogue of the well-studied di(2-pyridyl)amine (Hdpa) ligand, which was used to generate the first extended metal atom chain. Three types of coordination modes were found: anti-anti style which resulted in a mononuclear compound [Cu(Hdpza)(2)(H(2)O)(2)](ClO(4))(2) (2); anti-syn which was observed in a complex for the first time and resulted in a 2-D coordination polymer [Co(mu(2)-Hdpza)(2)(NCS)(2)] (3); and syn-syn type which was observed in extended metal atom chains [Ni(3)(mu(3)-dpza)(4)Cl(2)] (4), [Ni(3)(mu(3)-dpza)(4)(NCS)(2)] (5) and [Cr(3)(mu(3)-dpza)(4)Cl(2)] (6). Weak antiferromagnetic coupling via Hdpza was observed in 3, whereas magnetic studies on extended metal atom chains 4 and 5 revealed that the interaction parameter was more than -200 cm(-1). Electrochemistry showed that the extended metal atom chains 4-6 are much more stable to oxidation than the Hdpa complexes, and are able to undergo reduction.     

One-, two- and three-dimensional Cu(II) complexes built via new oligopyrazinediamine ligands: from antiferromagnetic to ferromagnetic coupling

Six new pyrazine-modulated N,N'-bis(alpha-pyridyl)-2,6-diaminopyridine ligands (PMN5) were synthesized and their complexes studied. Reaction of copper(II) with the ligand that contained one pyrazine ring in its terminal position led to formation of a one-dimensional zigzag complex whereas copper(II) reactions with ligands containing three pyrazine rings or one pyrazine ring in its middle position yielded straight one-dimensional complexes. A 2-D complex was produced from the ligand with two pyrazine rings at both terminals. When nickel(II) was introduced, a 3-D network was obtained from the three-pyrazine-modulated ligand. Researches on variable-temperature magnetic susceptibility measurements revealed excellent Heisenberg chains with weak antiferromagnetic interaction of J values from -2 to -3 cm(-1)viasigma and pi pathways in straight one-dimensional complexes between the Cu(II) centers separated by 6.8-6.9 A. The zigzag one-dimensional complex showed very poor magnetic coupling. The two-dimensional compound showed significant ferromagnetic interaction in spite of the Cu-Cu distance of 7.2 A. Ferromagnetic coupling was discussed and attributed to the unusual coordination mode of in-plane and out-of-plane linkage of bridging pyrazine rings. The three-dimensional heterometal Cu(II)-Ni(II) compound showed weak antiferromagnetic interaction, which was satisfactorily fitted with J=-2.4 cm(-1) following a one-dimensional theoretical model including MFA.     

A host-guest optical sensor for aliphatic amines based on lipophilic cyclodextrin

A host-guest optical sensor for the determination of aliphatic amines as exemplified by octylamine is proposed. It is based on the reversible fluorescence enhancement of heptakis(2,6-di-O-isobutyl)-β-cyclodextrin(DOB-β-CD) hosting tetraphenylporphyrin (TPP) immobilized in poly(vinyl chloride) (PVC) membrane by aliphatic amine extracted from aqueous phase into membrane phase. The optimum membrane contained 1.15 wt % TPP, 6.15 wt % DOB-β-CD as sensing reagent and other membrane materials. The fluorescence enhancement of the membrane resulted from the formation of a stable three-component complex among DOB-β-CD, TPP, and aliphatic amines. With the optimum conditions described, the fluorescence response of the sensor to octylamine shows a good correlation with the theoretically derived equation in the range 1.0 × 10^–6 to 8.0 × 10^–4 mol/L. The response characteristics including reversibility, response time, reproducibility and lifetime and selectivity of this optical device are also discussed in detail. This sensor has also been applied for the determination of octylamine in water samples containing interferents with satisfactory recovery.     

Synthetic magnetic opals

We present studies of novel nanocomposites of BiNi impregnated into the structure of opals as well as inverse opals. Atomic force microscopy and high resolution elemental analyses show a highly ordered structure and uniform distribution of the BiNi filler in the matrix. These BiNi-based nanocomposites are found to exhibit distinct ferromagnetic-like ordering with transition temperature of about 675 K. As far as we know there exists no report in literature on any BiNi compound which is magnetic.     

The crystallization kinetics of nanothin amorphous TlGa1 − x Ge x Se2 films

Crystallography Reports - The kinetics of phase transformations of amorphous Ge-doped TlGaSe2 films has been investigated by kinematic electron diffraction. It is shown that the crystallization of...     

Four quadruple metal-metal bonds lined up: linear nonachromium(II) metal string complexes

Through a new pyrazine-modulated penta-pyridyl-tetraamine ligand, H(4)N(9)-mpz, linear nonachromium(II) complexes with four quadruple metal-metal bonds were successfully obtained, and their structure, magnetic and electrochemistry properties were studied.     

Effect of Ultrasonic Treatment of Nanostructured Mn-Containing Catalyst for the Oxidation of Petroleum Hydrocarbons

Theoretical and Experimental Chemistry - The effect of ultrasonic treatment (UST) on the catalytic properties of a Mn-containing nanostructured carbon-based catalyst prepared by liquid-phase...