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421.
Amending the Anisotropy Barrier and Luminescence Behavior of Heterometallic Trinuclear Linear [MIILnIIIMII] (LnIII=Gd,Tb, Dy; MII=Mg/Zn) Complexes by Change from Divalent Paramagnetic to Diamagnetic Metal Ions 下载免费PDF全文
Dr. Sourav Das K. S. Bejoymohandas Atanu Dey Sourav Biswas Dr. M. L. P. Reddy Dr. Roser Morales Prof. Eliseo Ruiz Dr. Silvia Titos‐Padilla Prof. Enrique Colacio Prof. Vadapalli Chandrasekhar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6449-6464
The sequential reaction of a multisite coordinating compartmental ligand [2‐(2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylbenzylideneamino)‐2‐methylpropane‐1,3‐diol] (LH4) with appropriate lanthanide salts followed by the addition of [Mg(NO3)2] ? 6 H2O or [Zn(NO3)2] ? 6 H2O in a 4:1:2 stoichiometric ratio in the presence of triethylamine affords a series of isostructural heterometallic trinuclear complexes containing [Mg2Ln]3+ (Ln=Dy, Gd, and Tb) and [Zn2Ln]3+ (Ln=Dy, Gd, and Tb) cores. The formation of these complexes is demonstrated by X‐ray crystallography as well as ESI‐MS spectra. All complexes are isostructural possessing a linear trimetallic core with a central lanthanide ion. The comprehensive studies discussed involve the synthesis, structure, magnetism, and photophysical properties on this family of trinuclear [Mg2Ln]3+ and [Zn2Ln]3+ heterometallic complexes. [Mg2Dy]3+ and [Zn2Dy]3+ show slow relaxation of the magnetization below 12 K under zero applied direct current (dc) field, but without reaching a neat maximum, which is due to the overlapping with a faster quantum tunneling relaxation mediated through dipole–dipole and hyperfine interactions. Under a small applied dc field of 1000 Oe, the quantum tunneling is almost suppressed and temperature and frequency dependent peaks are observed, thus confirming the single‐molecule magnet behavior of complexes [Mg2Dy]3+ and [Zn2Dy]3+. 相似文献
422.
Single Crystal‐to‐Single Crystal Site‐Selective Postsynthetic Metal Exchange in a Zn–MOF Based on Semi‐Rigid Tricarboxylic Acid and Access to Bimetallic MOFs 下载免费PDF全文
Dr. Alankriti Bajpai Pujari Chandrasekhar Dr. Savitha Govardhan Dr. Rahul Banerjee Prof. Dr. Jarugu Narasimha Moorthy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2759-2765
The metal ions in a neutral Zn–MOF constructed from tritopic triacid H3L with inherent concave features, rigid core, and peripheral flexibility are found to exist in two distinct SBUs, that is, 0D and 1D. This has allowed site‐selective postsynthetic metal exchange (PSME) to be investigated and reactivities of the metal ions in two different environments in coordination polymers to be contrasted for the first time. Site‐selective transmetalation of Zn ions in the discrete environment is shown to occur in a single crystal‐to‐single crystal (SCSC) fashion, with metal ions such as Fe3+, Ru3+, Cu2+, Co2+, etc., whereas those that are part of 1D SBU sustain structural integrity, leading to novel bimetallic MOFs, which are inaccessible by conventional approaches. To the best of our knowledge, site‐selective postsynthetic exchange of an intraframework metal ion in a MOF that contains metal ions in discrete as well as polymeric SBUs is heretofore unprecedented. 相似文献
423.
Chandrasekhar V Gopal K Nagendran S Singh P Steiner A Zacchini S Bickley JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5437-5448
Organostannoxane-based multiredox assemblies containing ferrocenyl peripheries have been readily synthesized by a simple one-pot synthesis, either by a solution method or by room-temperature solid-state synthesis, in nearly quantitative yields. The number of ferrocenyl units in the multiredox assembly is readily varied by stoichiometric control as well as by the choice of the organotin precursors. Thus, the reaction of the diorganotin oxides, R2SnO (R = Ph, nBu and tBu) with ferrocene carboxylic acid affords tetra-, di-, and mononuclear derivatives [{Ph2Sn[OC(O)Fc]2}2] (1), [{[nBu2SnOC(O)Fc]2O}2] (2), [nBu2Sn{OC(O)Fc}2] (3), [{tBu2Sn(OH)OC(O)Fc}2] (4), and [tBu2Sn{OC(O)Fc}2] (5) (Fc = eta(5)C5H4-Fe-eta(5)C5H5). The reaction of triorganotin oxides, R3SnOSnR3 (R = nBu and Ph) with ferrocene carboxylic acid leads to the formation of the mono-nuclear derivatives [Ph3SnOC(O)Fc] (6) and [{nBu3SnOC(O)Fc}(n)] (7). Molecular structures of the compounds 1-4 and 6 have been determined by single-crystal X-ray analysis. The molecular structure of compound 1 is new among organotin carboxylates. In this compound, ferrocenyl carboxylates are involved in both chelating and bridging coordination modes to the tin atoms to form an eight-membered cyclic structure. In all of these compounds, the acidic protons of the cyclopentadienyl groups are hydrogen bonded to the carboxylate oxygens (C-HO) to form rich supramolecular assemblies. In addition to this, pi-pi, T-shaped, L-shaped, and side-to-face stacking interactions involving ferrocenyl groups also occur. Compound 6 shows an interesting and novel intermolecular CO2-pi stacking interaction. Electrochemical analysis of the compounds 1-4, 6, and 7 shows a single, quasi-reversible oxidation peak corresponding to the simultaneous oxidation of four, two, and one ferrocenyl substituents, respectively. Compound 5 shows two quasi-reversible oxidation peaks. This is attributed to the positional difference among the ferrocenyl substituents on the tin atom. Additionally, while compounds 2 and 4 are electrochemically quite robust and do not decompose even after ten continuous CV cycles, compounds 1, and 3, 5-7 start to show decomposition after five cycles. 相似文献
424.
A. Singh B. M. Rao G. R. Deshpande S. Sangaraju M. K. Srinivasu M. Lalitha Devi P. V. V. Satyanarayana K. B. Chandrasekhar 《Chromatographia》2007,65(3-4):191-196
A simple and rapid reversed-phase liquid chromatographic method was developed for the related substances determination and
quantitative evaluation of ziprasidone hydrochloride, which is used as an antipsychotic agent. Forced degradation studies
were performed on bulk sample of ziprasidone hydrochloride using acid, base, oxidative hydrolysis, thermal stress and photolytic
degradation. Mild degradation of the drug substance was observed during thermal stress and considerable degradation observed
during base hydrolysis. The chromatographic method was fine tuned using the samples generated from forced degradation studies.
Good resolution between the peaks corresponds to synthetic impurities and degradation products from the analyte were achieved
on YMC Pack Pro C18 column using the mobile phase consists of a mixture of 0.05% v/v of phosphoric acid in water and acetonitrile. The stressed test solutions were assayed against the qualified working standard
of ziprasidone hydrochloride and the mass balance in each case was close to 99.7% indicating that the developed method was
stability-indicating. Validation of the developed method was carried out as per ICH requirements. 相似文献
425.
Titanium dioxide was deposited from aqueous suspension onto cellulosic surfaces.Titania was sourced from Degussa (P25TM,70:30 anatase:rutile).Dry uptake of particles was shown to be rapid and dominant with one-third of the deposition occurring in less than 30 s and over one-half in the first minute.Isotherms were recorded to compare the rate of titanium deposition on dry and pre-wetted cotton.In the dry case uptake reached a maximum in 30 min whereas in the pre-wetted case the uptake was seen to continue beyond 180 min.A broad trend of higher deposition occurring at lower pH was seen,corresponding to the region where surface charges were opposite and thus attractive.Dry pickup was less significant at high pH.The response to varying ionic strength was complex and was attributed to the combined effect of charge screening,particle aggregation and consequent particle entrapment or occlusion.Titania deposition into the interstices of woven cotton sheets resulted in the formation of inorganic,nanoparticulate skeletons which could be isolated by controlled combustion of the cellulose and thus cotton was suggested to have potential for the templated synthesis of high surface area semiconductor materials. 相似文献
426.
Devi ML Chandrasekhar KB Surendranath KV Rao BM Narayana MB 《Journal of chromatographic science》2011,49(7):489-494
A validated specific stability indicating reversed-phase high-performance liquid chromatography method was developed for the quantitative determination of Amsacrine as well as its related substances determination in bulk samples, in presence of degradation products, and its process related impurities. Forced degradation studies were performed on bulk samples of Amsacrine as per International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human use (ICH) prescribed stress conditions using acid, base, oxidative, thermal stress, and photolytic degradation to show the stability indicating power of the method. Significant degradation was observed during basic hydrolysis, slight degradation was observed in oxidative and thermal stress, and no degradation was observed in other stress conditions. The chromatographic method was optimized using the samples generated from forced degradation studies and the impurity spiked solution. Good resolution between the peaks corresponds to process-related impurities and degradation products from the analyte were achieved on Inertsil ODS column using the mobile phase consists a mixture of 1.0% triethyl amine in 20 mM potassium dihydrogen orthophosphate, with pH adjusted to 6.5, with ortho phosphoric acid in water and acetonitrile using a simple linear gradient. The detection was carried out at wavelength 248 nm. The mass balance in each case was in between 99.4% to 99.9%, indicating that the developed method was stability-indicating. Validation of the developed method was carried out as per ICH requirements. The developed method was found to be suitable to check the quality of bulk samples of Amsacrine at the time of batch release and also during its stability studies. 相似文献
427.
Rama Krishna Ch Venkata Reddy Ch Udayachandran Thampy US Chandrasekhar AV Reddy YP Sambasiva Rao P Ravikumar RV 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2012,85(1):160-164
Chlorocadmiumphosphate Cd(HPO(4))Cl·[H(3)N(CH(2))(6)NH(3)](0.5) crystals containing Cu(II) ions have been successfully synthesized at room temperature by using organic amine 1,6-diamino hexane as a template. The samples are characterized by X-ray powder diffraction, Thermal and spectroscopic studies. These are crystallizes in the monoclinic crystal system with cell dimensions: a=1.7697, b=0.6576, c=1.9026nm and β=106.5°. FT-IR spectrum showed the absorption bands related to PO(4), NH(3)(+) ions and other organic molecule vibrations originated from the templated molecule. The prepared crystals are stable at room temperature and as well as up to around 300°C which were confirmed by thermal analysis. Optical absorption and EPR studies suggest that Cu(II) ion enters in to the lattice as tetragonally distorted octahedral symmetry, for which crystal field and spin-Hamiltonian parameters are calculated. Bonding parameters are suggesting that there exists partial covalent nature between Cu(II) ions and ligands. 相似文献
428.
An organocatalysis strategy has been developed toward the synthesis of O-spiro-C-aryl glycosides with different configurations in the sugar part. This strategy has been extended to the synthesis of the Papulacandin class of compounds. 相似文献
429.
The overall rate equation for a reaction sequence consisting of a pre-equilibrium and ratedetermining steps should not be
derived on the basis of the concentration of the intermediate product (X). This is apparently indicated by transition state
theory (as the path followed to reach the highest energy transition state is irrelevant), but also proved by a straight-forward
mathematical approach. The thesis is further supported by the equations of concurrent reactions as applied to the partitioning
of X between the two competing routes (reversal of the pre-equilibrium and formation of product). The rate equation may only
be derived rigorously on the basis of the law of mass action. It is proposed that the reactants acquire the overall activation
energy prior to the pre-equilibrium, thus forming X in a high-energy state en route to the rate-determining transition state. (It is argued that conventional energy profile diagrams are misleading and need
to be reinterpreted.) Also, these arguments invalidate the Michaelis-Menten equation of enzyme kinetics, and necessitate a
fundamental revision of our present understanding of enzyme catalysis. (The observed “saturation kinetics” possibly arises
from weak binding of a second molecule of substrate at the active site; analogous conclusions apply to reactions at surfaces). 相似文献
430.
M. SeenaiahS. Chandrasekhar 《Tetrahedron letters》2012,53(32):4087-4089
Stereoselective synthesis of the polyketide fragment commonly present in hoiamide A, B, and C is described using iterative Crimmins aldol reaction as the key reaction. 相似文献