Coordination asymmetry in μ-oxido divanadium complexes: Development of synthetic protocols

This brief review deals with the development of a general protocol for the synthesis of μ-oxido divanadium(V) compounds [LOV^V-(μ-O)-V^VO(Salen)] (L = L¹–L⁵) (1–5) incorporating coordination asymmetry. One of the vanadium centers in these compounds has an octahedral environment, completed by tetradentate Salen ligand, while the other center has a square pyramidal geometry, made up of tridentate biprotic Schiff-base ligands (H₂L^1–5) with ONO (1–3) and ONS (4, 5) type donor combinations. Single crystal X-ray diffraction, ESI-MS, and multi-nuclear NMR (¹H and ⁵¹V) spectroscopy have been used extensively for the characterization of these compounds. The V₂O₃ core in these compounds, save 3, has a rare type of twist-angular structure. The V(1)?V(2) separations (3.7921(7)–3.3084(6) Å) are by far the largest in these compounds compared to their peers containing a V₂O₃ core. The molecules retain their unsymmetrical binuclear structures also in solution as established by NMR spectroscopy. The mixed-oxidation compound (ImH)[L⁴OV^IV-(μ-O)-V^VOL⁵] 7 containing two dissimilar ligands has a V₂O₃ core with a syn-angular structure and exhibits crystallographically imposed mirror symmetry due to static disorder. In solution of donor solvents, this angular core structure changes into a linear one (anti-linear) by accepting solvents in to the vacant coordination site of the metal centers. Finally, the protocol for the synthesis of heterobimetallic compounds with vanadium(V) and Re(VII) combination flanked by a single μ-oxido bridge has been developed in which the precursor complexes [V^IVOL^6,7] (H₂L^6,7 are Salen type of ligands) are allowed to oxidize aerially in the presence of added perrhenate anion. The oxidized [V^VOL^6,7]⁺ species hold the ReO₄^? anion in the vacant coordination site of the metal ion, trans to the terminal oxido group, thus generating the V^V–O–Re^VII moiety in the heterobimetallic compounds (9 and 10). Both X-ray crystallography and ¹H NMR spectroscopy have been used to establish the identities of these compounds. In compound 9, the Re(1)–O(11)–V(1) bridge angle is barely linear (170.2(3)°) with a Re?V separation of 3.9647(9) Å. The redox behavior of 9 and 10 are quite interesting, each undergoing two reductions both in the positive potential range at E_1/2 = 0.59 and 0.16 V vs. Ag/AgCl reference and have single-electron stoichiometry, confirmed by constant potential coulometry.     

Charge delocalization in a homologous series of α,α'-bis(dianisylamino)-substituted thiophene monocations

A homologous series of three molecules containing thiophene, bithiophene, and terthiophene bridges between two redox-active tertiary amino groups was synthesized and explored. Charge delocalization in the one-electron-oxidized forms of these molecules was investigated by a combination of cyclic voltammetry, near-infrared optical absorption spectroscopy, and EPR spectroscopy. All three cation radicals can be described as organic mixed-valence species, and for all of them the experimental data are consistent with strong delocalization of the unpaired electron. Depending on what model is used for analysis of the optical absorption data, estimates for the electronic coupling matrix element (H(AB)) range from ～5000 to ～7000 cm(-1) for the shortest member of the homologous series. According to optical absorption and EPR spectroscopy, even the terthiophene radical appears to belong either to Robin-Day class III or to a category of radicals commonly denominated as borderline class II/class III systems. The finding of such a large extent of charge delocalization over up to three adjacent thiophene units is remarkable.     

分光光度滴定法测某些多齿配体与Ni(Ⅱ)配合物的稳定常数

制备了多齿大环配体1,4,7,10-四氮杂环十二烷(L1);1,4,8,11-四(2-羟乙基)-1,4,8,11-四氮杂环十四烷(L2)和无环多齿配体;3-(2-氨基环己氨基)-2-(2-氨基环己氨基甲基)丙酸(L3),4,7,10-十三烷二腈三氢氯化物(L4),2,2′-(1,2-二乙基-双((甲基二氮杂烷基)二乙醇(L5)and 1,1′-(1,2-二乙基-双((2-氨基乙基)二氮杂烷基))-2-二丙醇(L6),并用FTIR,NMR和MS进行了表征,用配有二极管阵列检测器、蠕动泵和pH计的UV-VIS光度仪,经分光光度滴定法测定了它们与Ni髤的配合物的稳定常数。将稳定常数的数据与配体的开链和环状结构特性进行了关联讨论。还讨论了侧基对配合物稳定常数的影响。     

Thermal pretreatment of silica composite filler materials

Three different silica filler materials were thermally treated in order to effect dehydration, dehydroxylation, and rehydroxylation. Samples were characterized by thermogravimetry (TG), pycnometry, elemental analysis, and scanning electron microscopy (SEM). For all fillers, our results indicate incremental removal of silanol groups at higher heating temperatures and irreversible dehydroxylation at over 673 K. To remove the organic content and maintain adequate silanol density for subsequent silanization on Stöber-type silica, we suggest heating at 673 K followed by overnight boiling in water.     

Vibrational Spectra of Arsenates and Phosphates of the Type Kcaln(XO4)2

The infrared and Raman spectra of polycrystal-line samples of different compounds of the types KCaLn(AsO₄)₂ and KCaLn(PO₄)₂, belonging to the hexagonal LaPO₄, structural modification, were recorded and discussed. A complete vibrational assignment, based on a factor group analysis, is proposed. The influence of the different lanthanide cations on the internal vibrations of the XO₄ groups is briefly discussed and some comparisons with related compounds are also made.

It is well known that simple lanthanide arsenates, phosphates, vanadates and cnromates (V) of the type LnXO₄ belong to two different structural types.     

Rank preservers of matrices over max algebra

The max algebra consists of the nonnegative real numbers equipped with two binary operations, maximization and multiplication. We consider the semimodules over max algebra and study the properties of the weak basis and weak dimension of the semi-modules. Moreover, we obtain the characterizations of those linear operators that preserve rank of matrices over max-algebra.     

Application of porous phosphate heterostructure materials for gas separation

In this study, the adsorbents Cu+-3SiPPH723 and Cu2+-3SiPPH723 were prepared starting from a silica-expanded zirconium phosphate heterostructure, 3SiPPH(0.2), which was subjected to an ion exchange with Cu(I) and Cu(II). These materials were characterized using powder X-ray diffraction, X-ray photoelectron spectroscopy, ammonia thermally programmed desorption, hydrogen temperature-programmed reduction, and N2 adsorption (77 K). The equilibria and kinetics of adsorption of pure propylene (C3H6) and propane (C3H8) were studied using a conventional glass high-vacuum volumetric device, equipped with grease-free valves, in the temperature range of 273-393 K. The starting material, 3SiPPH(0.2), presented a high acidity and irreversible chemisorption of the olefin, which increases with temperature. Unlike the support, the irreversible adsorption of the olefin on the Cu+-3SiPPH723 and Cu2+-3SiPPH723 samples decreases with increasing temperature and disappears at 393 K, showing a very high selectivity toward propylene. The C3H8 adsorption in all the samples was always reversible. On the basis of the results of this study, both Cu+-3SiPPH723 and Cu2+-3SiPPH723 samples can be efficiently applied in the separation of a C3H6/C3H8 mixture at 393 K. Cu+-3SiPPH723 would have the highest efficiency, because its capacity for C3H6 adsorption was higher than that for the Cu2+-3SiPPH723 sample.     

Multiple topologies from glycopolypeptide-dendron conjugate self-assembly: nanorods, micelles, and organogels

Glycopolypeptides (GPs) were synthesized by ring-opening polymerization of glycosylated N-carboxyanhydride monomer and attached to hydrophobic dendrons at one chain end by "click" reaction to obtain amphiphilic anisotropic macromolecules. We show that by varying polypeptide chain length and dendron generation, an organogel was obtained in dimethylsulfoxide, while nanorods and micellar aggregates were observed in aqueous solutions. Assemblies in water were characterized by electron microscopy and dye encapsulation. Secondary structure of the GP chain was shown to affect the morphology, whereas the chain length of the poly(ethylene glycol) linker between the GP and dendron did not alter rod-like assemblies. Bioactive surface chemistry of these assemblies displaying carbohydrate groups was demonstrated by interaction of mannose-functionalized nanorods with ConA.