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941.
942.
943.
Synthesis and some first-row transition-metal complexes of the 1,2,4-triazole-based Bis(terdentate) ligands TsPMAT and PMAT 总被引:1,自引:0,他引:1
Klingele MH Moubaraki B Murray KS Brooker S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):6962-6973
The employment of a strategy based on nucleophilic substitution, rather than Schiff base condensation, for the preparation of 1,2,4-triazole-based ligands has been investigated and has led to the synthesis of two new ligands, 4-amino-3,5-bis{[N-(2-pyridylmethyl)-N-(4-toluenesulfonyl)amino]methyl}-4H-1,2,4-triazole (TsPMAT, 14) and 4-amino-3,5-bis{[(2-pyridylmethyl)amino]methyl}-4H-1,2,4-triazole (PMAT, 15). These are the first examples of bis(terdentate) ligands incorporating the 1,2,4-triazole unit. TsPMAT (14) forms a dinuclear 2:2 complex with Co(BF4)2.6 H2O even when reacted in a metal-to-ligand molar ratio of 2:1. Similarly, the reaction of PMAT (15) with Mn(ClO4)2.6H2O or M(BF4)2.6 H2O (M=Fe, Co, Ni, Zn) in a ligand-to-metal molar ratio of 1:1 has afforded a series of complexes with the general formula [M(II) (2)(PMAT)2]X4. The metal centres in these complexes of TsPMAT (14) and PMAT (15) are encapsulated by two ligand molecules and doubly bridged by the N2 units of the 1,2,4-triazole moieties, which gives rise to N6 coordination spheres that are strongly distorted from octahedral, as evidenced by the X-ray crystal structure analyses of [Co(II) (2)(TsPMAT)(2)](BF(4))(4)6 MeCN (246 MeCN) and [Fe(II) 2(PMAT)2](BF4)4DMF (27DMF). Studies of the magnetic properties of [Co(II) 2(TsPMAT)2](BF4)4.4 H2O (244 H2O), [Mn(II) 2(PMAT)2](ClO4)4 (26), and [Co(II) 2(PMAT)2](BF4)4 (28) have revealed weak antiferromagnetic coupling (J=-3.3, -0.16, and -2.4 cm(-1), respectively) between the two metal centres in these complexes. 相似文献
944.
Vadim A. Medvedev Michael E. Efimov Paul J. Cerutti Robert M. McKay Lawrence H. Johnson Loren G. Hepler 《Thermochimica Acta》1978,23(1):87-92
We have made calorimetric measurements of the enthalpy of solution of NH4NO3(c, IV) in water at 298 K, where (c, IV) indicates the crystal form of amomonium nitrate that is stable from 256 to 305 K. Results of our measurements have been combined with enthalpy of dilution values from Parker to obtain the standard enthalpy of solution of NH4NO3 (c, IV) in water at 298.15 K to be ΔHo = 25.41 kJ mol?1. 相似文献
945.
The electron spin-Lattice relaxation, (SLR) rate constants have been measured for the triplet state at pyrazine-d4 in a cyclohexane matrix from 1 to 8 K by resolving the phosphorescent decay curve into three exponential components. A matrix kinetics is presented that gives the relationship between the SLR rate constants and the observed decay component rate constants and the decay component intensities of the three zero-field levels. An exact numerical procedure based on the Newton-Raphson technique is described in detail for systems of two and three coupled levels. This procedure was used to find the SLR rate constants starting from either the decay component rate constants or the decay component intensities. Both the matrix kinetics and the numerical procedure should be useful in many other studies involving multilevel systems whose sublevels are connected by some combination of SLR and microwaves. The observed SLR rate constants are best explained as a function of temperature as the sum of a direct process (linear in T) and a Raman process (T2 dependence). Their relative magnitudes indicate that the Raman process is probably antharmonic. Vancus mechanisms for SLR in this system are examined, and a short review of SLR theory and experiment is given. The nature of the zero-field sublevels in pyrazine-J4 is also discussed as is the effect of the choice of matrix solvent upon SLR rate constants and the phosphorescent spectrum. 相似文献
946.
Mohsen Asadnia Matthew Myers N.D. Akhavan Kane O'Donnell Gilberto A. Umana-Membreno U.K. Mishra Brett Nener Murray Baker Giacinta Parish 《Analytica chimica acta》2016
This work presents the first polymer approach to detect metal ions using AlGaN/GaN transistor-based sensor. The sensor utilised an AlGaN/GaN high electron mobility transistor-type structure by functionalising the gate area with a polyvinyl chloride (PVC) based ion selective membrane. Sensors based on this technology are portable, robust and typically highly sensitive to the target analyte; in this case Hg2+. This sensor showed a rapid and stable response when it was introduced to solutions of varying Hg2+ concentrations. At pH 2.8 in a 10−2 M KNO3 ion buffer, a detection limit below 10−8 M and a linear response range between 10−8 M-10−4 M were achieved. This detection limit is an order of magnitude lower than the reported detection limit of 10−7 M for thioglycolic acid monolayer functionalised AlGaN/GaN HEMT devices. Detection limits of approximately 10−7 M and 10−6 M in 10−2 M Cd(NO3)2 and 10−2 M Pb(NO3)2 ion buffers were also achieved, respectively. Furthermore, we show that the apparent gate response was near-Nernstian under various conditions. X-ray photoelectron spectroscopy (XPS) experiments confirmed that the sensing membrane is reversible after being exposed to Hg2+ solution and rinsed with deionised water. The success of this study precedes the development of this technology in selectively sensing multiple ions in water with use of the appropriate polymer based membranes on arrays of devices. 相似文献
947.
Anniefer N. Magpusao Kelli Rutledge Dr. Trevor A. Hamlin Jean‐Marc Lawrence Dr. Brandon Q. Mercado Prof. Nicholas E. Leadbeater Prof. Mark W. Peczuh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):6001-6011
Shape is an inherent trait of a molecule that dictates how it interacts with other molecules, either in binding events or intermolecular reactions. Large‐ring macrocyclic compounds in particular leverage their shape when they are selectively bound by biomolecules and also when they exhibit macrocyclic diastereoselectivity. Nonetheless, rules that link structural parameters to the conformation of a macrocycle are still rudimentary. Here we use a structural investigation of a family of [13]‐macrodilactones as a case study to develop rules that can be applied generally to macrocycles of different sizes and with a variety of functionality. A characteristic “ribbon” shape is adopted by the [13]‐macrodilactones in the absence of stereogenic centres, which exhibits planar chirality. When one stereogenic centre at key positions on the backbone is incorporated into the structure, the planar chirality is dictated by the configuration of the centre. In cases where two stereogenic centres are present, their relationships can either reinforce the characteristic ribbon shape or induce alternative shapes to be adopted. The rules established in the case study are then applied to the analysis of a structure of the natural product migrastatin. They lay the groundwork for the development of models to understand macrocycle‐biomolecule interactions and for the preparation of macrocycles with designed properties and activities. 相似文献
948.
949.
950.
Lawrence B. Alemany 《Magnetic resonance in chemistry : MRC》2013,51(10):605-613
New information has been obtained from very‐high‐resolution 13C NMR studies of a series of long‐chain n‐alkanes. These compounds are fundamentally important in the petroleum industry and are essential to the life of some plants, flowers, and insects. At least partial resolution of the ten different 13C NMR signals of n‐C20H42 is observed at 11.7 T for solutions in C6D6 or C6D5CD3. A 13C T1 inversion‐recovery experiment provides much more detailed information than in previous studies of long‐chain n‐alkanes, demonstrates a steady increase in the relaxation times of the ten different carbons proceeding from the middle to the end of the chain because of segmental motion, and thus confirms the assignments for the interior carbons. In contrast, there is significant overlap for the signals for C‐7 and the more interior carbons in a solution of n‐C16 or longer chain alkanes in CDCl3. Not only are the chemical shifts sensitive to the solvent used, but also the relative chemical shifts change. Signals for the interior carbons of the odd‐number alkanes in CDCl3 are better resolved than in the spectra of their even‐number counterparts. Some mixed aromatic solvent systems give increased dispersion of the cluster of C‐6 through C‐10 signals of n‐C20H42, n‐C21H44, and n‐C22H46. However, none of the solvents used could even partially resolve the C‐10 and C‐11 signals of n‐C21H44 or n‐C22H46 at 11.7 T, which may result from a different distribution of conformers for n‐C21H44 or n‐C22H46 than for n‐C20H42 and shorter n‐alkanes. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献