Three-dimensional mesomeric networks assembled from helix-linked sheets: syntheses, structures, and magnetisms

Two new three-dimensional nickel coordination polymers, [Ni3(BTC)2(4,4'-bpy)2(H2O)5].1.5H2O (1) and [Ni(PDB)(4,4'-bpy)].0.5H2O (2)(4,4'-bpy = bipyridine, BTC = 1,2,4-benzenetricarboxylate, PDB = pyridine-3,4-dicarboxylate), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TGA, and single crystal X-ray diffraction. Both compounds contain 2D scaffolding motifs, and most interestingly adjacent scaffolds are connected by infinite helical chains into unique three-dimensional mesomeric networks. Moreover, temperature-dependent magnetic susceptibilities for the two compounds were studied, and ferromagnetic interactions through syn-anti carboxylate bridges between Ni sites have been observed.     

Linear NiII-MnIII2-NiII tetramers: an oligomeric component of the MnIII2NiII single-chain magnets

Heterometallic linear tetramers [Mn(5-R-saltmen)Ni(pao)(bpy)(2)](2)(ClO(4))(4) (5-R-saltmen(2-) = N,N'-1,1,2,2-tetramethylethylene bis(5-R-salicylideneiminate); pao(-) = pyridine-2-aldoximate; bpy = 2,2'-bipyridine, R = H, 1; Cl, 2; Br, 3; MeO, 4) have been synthesized and structurally characterized. These compounds exhibit a [Ni(II)-NO-Mn(III)-(O)(2)-Mn(III)-ON-Ni(II)] skeleton where -ON- is an oximate bridge between Mn(III) and Ni(II) ions and -(O)(2)- is a bi-phenolate bridge between Mn(III) ions. These tetramers can be seen as oligomeric units of the heterometallic Mn(III)(2)-Ni(II) chain observed in a family of single-chain magnets (Clérac, R.; Miyasaka, H.; Yamashita, M.; Coulon, C. J. Am. Chem. Soc. 2002, 124, 12837. Miyasaka, H.; Clérac, R.; Mizushima, K.; Sugiura, K.; Yamashita, M.; Wernsdorfer, W.; Coulon, C. Inorg. Chem. 2003, 42, 8203.). Magnetic measurements on these tetramers confirm the nature of the magnetic interactions reported for the Mn(III)(2)-Ni(II) chains: a strong antiferromagnetic Mn(III)/Ni(II) coupling via the oximate bridge (J(Ni-Mn) ranges from -23.7 to -26.1 K) and a weak ferromagnetic Mn(III)/Mn(III) coupling through the bi-phenolate bridge (J(Mn-Mn) ranges from +0.4 to +0.9 K). These magnetic interactions lead to tetramers with an S = 2 ground state.     

MnIII2 (5-Rsaltmen)2NiII(pao)2(L)]2+: an S(T)=3 building block for a single-chain magnet that behaves as a single-molecule magnet

Mn(III)-Ni(II)-Mn(III) linear-type trinuclear complexes bridged by oximate groups were selectively synthesized by the assembly reaction of [Mn2(5-Rsaltmen)2(H2O)2](ClO4)2 (5-Rsaltmen2-=N,N'-(1,1,2,2-tetramethylethylene) bis(5-R-salicylideneiminate); R=Cl, Br) with [Ni(pao)2(phen)] (pao-=pyridine-2-aldoximate; phen=1,10-phenanthroline) in methanol/water: [Mn2(5-Rsaltmen)2Ni(pao)2(phen)](ClO4)2 (R=Cl, 1; R=Br, 2). Structural analysis revealed that the [Mn(III)-ON-Ni(II)-NO-Mn(III)] skeleton of these trimers is in every respect similar to the repeating unit found in the previously reported series of 1D materials [Mn2(saltmen)2Ni(pao)2(L1)2](A)(2) (L(1)=pyridine, 4-picoline, 4-tert-butylpyridine, N-methylimidazole; A=ClO4-, BF4-, PF6-, ReO4-). Recently, these 1D compounds have attracted a great deal of attention for their magnetic properties, since they exhibit slow relaxation of the magnetization (also called single-chain magnet (SCM) behavior). This unique magnetic behavior was explained in the framework of Glauber's theory, generalized for chains of ferromagnetically coupled anisotropic spins. Thus, in these 1D compounds, the [Mn(III)-ON-Ni(II)-NO-Mn(III)] unit was considered as an S(T)=3 anisotropic spin. Direct-current magnetic measurements on 1 and 2 confirm their S(T)=3 ground state and strong uniaxial anisotropy (D/k(B) approximately -2.4 K), in excellent agreement with the magnetic characteristic deduced in the study on the SCM series. The ac magnetic susceptibility of these trimers is strongly frequency-dependent and characteristic of single-molecule magnet (SMM) behavior. The relaxation time tau shows a thermally activated (Arrhenius) behavior with tau0 approximately 1x10(-7) s and Delta(eff)/k(B) approximately 18 K. The effective energy barrier for reversal of the magnetization Delta(eff) is consistent with the theoretical value (21 K) estimated from |D| S2T. The present results reinforce consistently the interpretation of the SCM behavior observed in the [Mn2(saltmen)2Ni(pao)2(L1)2](A)2 series and opens new perspectives to design single-chain magnets.     

A novel octanuclear Mn(III) aggregate as a single-molecule magnet

The novel octanuclear cluster [Mn8O2(OH)2(OMe)12(OAc)2(Mesalim)4] (1) presents SMM behaviour with a relatively high experimental energy barrier (eff/kB= 36.0 K) as shown by its dc and ac magnetic properties.     

Electronic structure and solvation of copper and silver ions: a theoretical picture of a model aqueous redox reaction

Electronic states and solvation of Cu and Ag aqua ions are investigated by comparing the Cu(2+) + e(-)--> Cu(+) and Ag(2+) + e(-)--> Ag(+) redox reactions using density functional-based computational methods. The coordination number of aqueous Cu(2+) is found to fluctuate between 5 and 6 and reduces to 2 for Cu(+), which forms a tightly bound linear dihydrate. Reduction of Ag(2+) changes the coordination number from 5 to 4. The energetics of the oxidation reactions is analyzed by comparing vertical ionization potentials, relaxation energies, and vertical electron affinities. The model is validated by a computation of the free energy of the full redox reaction Ag(2+) + Cu(+) --> Ag(+) + Cu(2+). Investigation of the one-electron states shows that the redox active frontier orbitals are confined to the energy gap between occupied and empty states of the pure solvent and localized on the metal ion hydration complex. The effect of solvent fluctuations on the electronic states is highlighted in a computation of the UV absorption spectrum of Cu(+) and Ag(+).     

Octasubstituted metal-free phthalocyanine as core of phosphorus dendrimers: a probe for the properties of the internal structure

The synthesis of a new family of phosphorus dendrimers built from an octasubstituted metal-free phthalocyanine core is described up to generation 5. This core is used as a sensor and a probe for analyzing the properties of the internal structure and the influence of each structural part (core, branches, surface) upon the whole structure. UV-visible spectra show both a hyperchromic and bathochromic effect on the Q-bands with increasing generation, indicating that the chromophore is more isolated, and that the dendritic shell mimics a highly polar solvent. There is no evidence for aggregation, except for generation 0, showing again the isolation of the core. However, the dendritic shell is permeable to aqueous acids and bases, as demonstrated by the reversible splitting of the Q-band in an acidic medium (neutral form of the phthalocyanine) and the single Q-band in a basic medium (dianionic form), even for generation 4. The fluorescence quantum yield for the neutral form increases with increasing generation. The dianionic form of generation 0 is poorly fluorescent, whereas generations 3 and 4 (G3 and G4) exhibit better fluorescence. The cores of G3 and G4 are highly sensitive optical sensors for H3O+ and OH-. These experiments are carried out in THF/water mixtures, and the influence of water on the structure has been checked. The hydrodynamic radius of generation 4 is measured by NMR diffusion (pulse gradient spin-echo) experiments. R(H) varies from 35.4 A at 4 mol % of water to 32.5 A at 64 mol % of water in THF, indicating the hydrophobic nature of these dendrimers.     

Templating S100A9 amyloids on Aβ fibrillar surfaces revealed by charge detection mass spectrometry,microscopy, kinetic and microfluidic analyses

The mechanism of amyloid co-aggregation and its nucleation process are not fully understood in spite of extensive studies. Deciphering the interactions between proinflammatory S100A9 protein and Aβ₄₂ peptide in Alzheimer''s disease is fundamental since inflammation plays a central role in the disease onset. Here we use innovative charge detection mass spectrometry (CDMS) together with biophysical techniques to provide mechanistic insight into the co-aggregation process and differentiate amyloid complexes at a single particle level. Combination of mass and charge distributions of amyloids together with reconstruction of the differences between them and detailed microscopy reveals that co-aggregation involves templating of S100A9 fibrils on the surface of Aβ₄₂ amyloids. Kinetic analysis further corroborates that the surfaces available for the Aβ₄₂ secondary nucleation are diminished due to the coating by S100A9 amyloids, while the binding of S100A9 to Aβ₄₂ fibrils is validated by a microfluidic assay. We demonstrate that synergy between CDMS, microscopy, kinetic and microfluidic analyses opens new directions in interdisciplinary research.

Templating mechanism of S100A9 amyloids on Aβ fibrillar surfaces during amyloid co-aggregation process was revealed by synergy of biophysical methods including charge detection mass spectrometry, microscopy, kinetic and microfluidic analyses.     

Copper-Photocatalyzed Borylation of Organic Halides under Batch and Continuous-Flow Conditions

The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (Cu^I/Cu^I*/Cu⁰) was suggested.     

Stabilité analytique et convergence locale de translatées en dynamique homogène S-arithmétique

We present the main result of Richard and Zamojski [14] concerning, in homogeneous dynamics, the general problem of the dynamics of sequences of translates of a certain measure in a space of S-arithmetic lattices.