Shuttling of nickel oxidation states in N4S2 coordination geometry versus donor strength of tridentate N2S donor ligands

Seven bis-Ni(II) complexes of a N(2)S donor set ligand have been synthesized and examined for their ability to stabilize Ni(0), Ni(I), Ni(II) and Ni(III) oxidation states. Compounds 1-5 consist of modifications of the pyridine ring of the tridentate Schiff base ligand, 2-pyridyl-N-(2'-methylthiophenyl)methyleneimine ((X)L1), where X = 6-H, 6-Me, 6-p-ClPh, 6-Br, 5-Br; compound 6 is the reduced amine form (L2); compound 7 is the amide analog (L3). The compounds are perchlorate salts except for 7, which is neutral. Complexes 1 and 3-7 have been structurally characterized. Their coordination geometry is distorted octahedral. In the case of 6, the tridentate ligand coordinates in a facial manner, whereas the remaining complexes display meridional coordination. Due to substitution of the pyridine ring of (X)L1, the Ni-N(py) distances for 1~5 < 3 < 4 increase and UV-vis λ(max) values corresponding to the (3)A(2g)(F)→(3)T(2g)(F) transition show an increasing trend 1~5 < 2 < 3 < 4. Cyclic voltammetry of 1-5 reveals two quasi-reversible reduction waves that correspond to Ni(II)→Ni(I) and Ni(I)→Ni(0) reduction. The E(1/2) for the Ni(II)/Ni(I) couple decreases as 1 > 2 > 3 > 4. Replacement of the central imine N donor in 1 by amine 6 or amide 7 N donors reveals that complex 6 in CH(3)CN exhibits an irreversible reductive response at E(pc) = -1.28 V, E(pa) = +0.25 V vs saturated calomel electrode (SCE). In contrast, complex 7 shows a reversible oxidation wave at E(1/2) = +0.84 V (ΔE(p) = 60 mV) that corresponds to Ni(II)→Ni(III). The electrochemically generated Ni(III) species, [(L3)(2)Ni(III)](+) is stable, showing a new UV-vis band at 470 nm. EPR measurements have also been carried out.     

A heterometallic (Ni(II)-Cu(II)) decanuclear cluster containing two distorted cubane-like pentanuclear cores: synthesis, structure, and magnetic properties

A new heterometallic Ni(II)-Cu(II) decanuclear cluster, {[Ni(4)Cu(6)(μ-OH(2))(2)(dpkO(2))(8)(OAc)(4)(H(2)O)(4)]·2CH(3)OH·17H(2)O} (1), has been synthesized by self-assembly of the constituent metal ions and the precursor di-2-pyridylketone (dpk) of multinucleating ligand dpkO(2)(2-) and is structurally characterized. The cluster 1 is formed by the union of two symmetry-related distorted cubane-like pentanuclear cores. A magnetic study of 1 reveals strong antiferromagnetic interactions operating through the Ni-O-Ni pathway, which is independent of the assumption D = 0 or D ≠ 0. The pentanuclear cores are ferromagnetically coupled, as supported by density functional theory calculations.     

A new colorimetric chemodosimeter for mercury ion via specific thioacetal deprotection in aqueous solution and living cells

A sensitive and selective new chemodosimeteric chemosensor (DIBT) for mercury ions was successfully devised and characterized. Upon addition of Hg²⁺ to DIBT, a red-edge absorption band at 972 nm was observed. An important feature for the new chemodosimeter is its high selectivity toward mercury ions over the other competitive species due to Hg²⁺-triggered specific C–S cleavage, making the ‘naked-eye’ detection of mercury ions possible in aqueous solution and living cells such as Candida albicans.     

Metal-induced reductive ring opening of 1,2,4,5-tetrazines: three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system

Reaction of 3,6-diaryl-1,2,4,5-tetrazines (aryl = R = phenyl, 2-furyl or 2-thienyl) with 2 equiv of Ru(acac)2(CH3CN)2 results in reductive tetrazine ring opening to yield diruthenium complexes [(acac)2Ru(III)(dih-R(2-))Ru(III)(acac)2] bridged by the new 1,2-diiminohydrazido(2-) (dih-R(2-) = HNC(R)NNC(R)NH(2-)) ligands. rac/meso diastereoisomers could be detected and separated for the compounds with R = phenyl and 2-thienyl, all species are diamagnetic and were characterized by 1H NMR spectroscopy. Crystal structure determination of the meso isomers with R = phenyl and 2-thienyl confirmed the 1,2-diiminohydrazido formulation through long N-N (approximately 1.40 A) and short C=N(H) bonds (approximately 1.31 A), implying two bridged ruthenium(III) centers at about 4.765 A distance with strong antiferromagnetic coupling. The complexes undergo two reversible and well-separated one-electron reduction and oxidation processes, respectively. EPR Spectroscopy of the paramagnetic intermediates with comproportionation constants K(c) > 10(12) and UV-vis-NIR spectroelectrochemistry were used to identify the accessible redox states as [(acac)2Ru(II)(dih-R(2-))Ru(II)(acac)2]2-, [(acac)2Ru(II)(dih-R(*-))Ru(II)(acac)2]-, [(acac)2Ru(III)(dih-R(2-))Ru(III)(acac)2], [(acac)2Ru(III)(dih-R(*-))Ru(III)(acac)2]+, and [(acac)2Ru(III)(dih-R)Ru(III)(acac)2]2+. While the UV-vis-NIR spectroscopic response of [(acac)2Ru(dih-R)Ru(acac)2](0/-/2-) is very similar to that of [(bpy)2Ru(adc-R)Ru(bpy)2](4+/3+/2+), adc-R(2-) = 1,2-diacylhydrazido(2-), the EPR result indicating ligand-centered spin for [(acac)2Ru(II)(dih-R(*-))Ru(II)(acac)2]- despite deceptive NIR absorptions around 1400 nm reveals distinct differences in the electronic structures.     

Unsteady MHD Couette flow in a rotating system

The unsteady hydromagnetic Couette flow of a viscous incompressible electrically conducting fluid in a rotating system has been considered. An exact solution of the governing equations has been obtained by using a Laplace transform. Solutions for the velocity distributions as well as shear stresses have been obtained for small times as well as for large times. It is found that for large times the primary velocity decreases with increase in the rotation parameter K² while it increases with increase in the magnetic parameter M². It is also found that with increase in K², the secondary velocity v₁ decreases near the stationary plate while it increases near the moving plate. On the other hand, the secondary velocity decreases with increase in the magnetic parameter.     

A New Compound for Sequential Sensing of Picric Acid and Aliphatic Amines: Physicochemical Details and Construction of Molecular Logic Gates

Picric acid (PA) at low concentration is a serious water pollutant. Alongside, aliphatic amines (AAs) add to the queue to pollute surface water. Plenty of reports are available to sense PA with an ultralow limit of detection (LOD). However, only a handful of works are testified to detect AAs. A new fluorescent donor-acceptor compound has been synthesized with inherent intramolecular charge transfer (ICT) character that enables selective and sensitive colorimetric quantitative detection of PA and AAs with low LODs in non-aqueous as well as aqueous solutions. The synthesized compound is based on a hemicyanine skeleton containing two pyridenylmethylamino groups at the donor and a benzothiazole moiety at the acceptor ends. The detailed mechanisms and reaction dynamics are explained spectroscopically along with computational support. The fluorescence property of the detecting compound changes due to protonation of its pyridinyl centers by PA leading to quenching of fluorescence and subsequently de-protonation by AAs to revive the signal. We have further designed logic circuits from the acquired optical responses by sequential interactions.     

Effect of indium doping on thermal stability and dielectric property in sodium beta alumina solid electrolyte

Journal of Solid State Electrochemistry - We report the effect of indium doping on thermal stability and ionic conductivity of beta alumina NaInxAl11-xO17 solid electrolyte which is synthesized by...