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161.
Somnath Roy Tarak Nath Mandal Anil Kumar Barik Samik Gupta Ray J. Butcher Mohamed Salah El Fallah Javier Tercero Susanta Kumar Kar 《Polyhedron》2008
The synthesis and structure of a pyrazole-based orthogonal ferromagnetically coupled tetracopper(II) 2 × 2 homoleptic grid complex [Cu4(PzOAPyz)4(ClO4)2](ClO4)2 · 6H2O (1), formed by the reaction between the ditopic ligand PzOAPyz and Cu(ClO4)2 · 6H2O, are described. The ligand contains terminal pyrazole and pyrazine residues bound to a central flexible diazine subunit (N–N) as well as one potentially bridging alkoxo group. The two adjacent metal centers are linked by an alkoxo oxygen forming essentially a square Cu4(μ-O4) cluster. In the Cu4(μ-O4) core, out of the four copper centers, two copper centers are penta-coordinated and the remaining two are hexa-coordinated. In each case of hexa-coordination, the sixth position is occupied by one of the oxygen atoms of a coordinated perchlorate ion. Complex 1 has been characterized structurally and magnetically. Although the large Cu–O–Cu bridge angles (137–138°) and short Cu–Cu distances (3.964–3.970 Å) are suitable for the transmission of the expected antiferromagnetic coupling, the square-based Cu4(μ-O4) cluster exhibits an intramolecular ferromagnetic exchange (J = 7.47 cm−1) between the metal centers with an S = 2 magnetic ground state associated with the quasi orthogonal arrangement of the magnetic orbitals (dx2-y2). The exchange pathway parameters have been evaluated from density functional calculations. 相似文献
162.
Dr. Manju P. Maman Dr. Tamilselvi Gurusamy Dr. Arun K. Pal Dr. Rajkumar Jana Dr. Kothandaraman Ramanujam Dr. Ayan Datta Dr. Sukhendu Mandal 《Angewandte Chemie (International ed. in English)》2023,62(27):e202305462
The fixing of N2 to NH3 is challenging due to the inertness of the N≡N bond. Commercially, ammonia production depends on the energy-consuming Haber-Bosch (H−B) process, which emits CO2 while using fossil fuels as the sources of hydrogen and energy. An alternative method for NH3 production is the electrochemical nitrogen reduction reaction (NRR) process as it is powered by renewable energy sources. Here, we report a tiara-like nickel-thiolate cluster, [Ni6(PET)12] (where, PET=2-phenylethanethiol)] as an efficient electro-catalyst for the electrochemical NRR at ambient conditions. Ammonia (NH3: 16.2±0.8 μg h−1 cm−2) was the only nitrogenous product over the potential of −2.3 V vs. Fc+/Fc with a Faradaic efficiency of 25%±1.7. Based on theoretical calculations, NRR by [Ni6(PET)12] proceeds through both the distal and alternating pathways with an onset potential of −1.84 V vs. RHE (i.e., −2.46 V vs. Fc+/Fc) which corroborates with the experimental findings. 相似文献
163.
Dinda E Si S Kotal A Mandal TK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(18):5528-5537
A series of newly designed ascorbic acid based room temperature ionic liquids were successfully used to prepare quasi-spherical and anisotropic gold nanostructures in an aqueous medium at ambient temperature. The synthesis of these room temperature ionic liquids involves, first, the preparation of a 1-alkyl (such as methyl, ethyl, butyl, hexyl, octyl, and decyl) derivative of 3-methylimidazolium hydroxide followed by the neutralization of the derivatised product with ascorbic acid. These ionic liquids show significantly better thermal stability and their glass transition temperature (Tg) decreases with increasing alkyl chain length. The ascorbate counter anion of these ionic liquids acts as a reducing agent for HAuCl4 to produce metallic gold and the alkylated imidazolium counter cation acts as a capping/shape-directing agent. It has been found that the nature of the ionic liquids and the mole ratio of ionic liquid to HAuCl4 has a significant effect on the morphology of the formed gold nanostructures. If an equimolar mixture of ionic liquid and HAuCl4 is used, predominantly anisotropic gold nanostructures are formed and by varying the alkyl chain length attached to imidazolium cation of the ionic liquids, various particle morphologies can formed, such as quasispherical, raspberry-like, flakes or dendritic. A probable formation mechanism for such anisotropic gold nanostructures has been proposed, which is based on the results of some control experiments. 相似文献
164.
Gurumurthy Hegde Govindaswamy Shanker S. M. Gan A. R. Yuvaraj Syed Mahmood Uttam Kumar Mandal 《Liquid crystals》2016,43(11):1578-1588
Azobenzene derivatives containing phenyl/4-halogen-phenyl 4-{(E)-[4-(pent-4-en-1-yloxy)phenyl]diazenyl}benzoate group with different electronegative substituent (H, F, Cl, Br and I) at other end was synthesised. These azo-based benzoate derivatives have been characterised by FTIR, 1H-NMR, 13C-NMR, elemental analyser, POM and UV-Vis spectroscopy. Photosaturation at 358 nm obtained after 82 s of UV irradiation and the longest thermal back relaxation time of 45 h recorded by UV-Vis. The azo derivative could be possible photolock under UV light, as observed by the improved thermal back relaxation time. The resulting photolockable chain of azobenzene might prove valuable in the development of optical device application. These azobenzene moieties also exhibit liquid crystalline behaviour with respect to the halogen substitution as an electron withdrawing group shows that strong structure property relationship exists among them. 相似文献
165.
Md. Sayem Alam R. Ragupathy Asit Baran Mandal 《Journal of Dispersion Science and Technology》2016,37(11):1645-1654
In the present study, we investigate the self-association and mixed micellization of an anionic surfactant, sodium dodecyl sulfate (SDS), and a cationic surfactant, cetyltrimethylammonium bromide (CTAB). The critical micelle concentration (CMC) of SDS, CTAB, and mixed (SDS + CTAB) surfactants was measured by electrical conductivity, dye solubilization, and surface tension measurements. The surface properties (viz., C20 (the surfactant concentration required to reduce the surface tension by 20 mN/m), ΠCMC (the surface pressure at the CMC), Γmax (maximum surface excess concentration at the air/water interface), and Amin (the minimum area per surfactant molecule at the air/water interface)) of SDS, CTAB, and (SDS + CTAB) micellar/mixed micellar systems were evaluated. The thermodynamic parameters of the micellar (SDS and CTAB), and mixed micellar (SDS + CTAB) systems were evaluated.A schematic representation of micelles and mixed micelles. 相似文献
166.
Soham Mandal Marian Hebenbrock Jens Müller 《Angewandte Chemie (International ed. in English)》2016,55(50):15520-15523
The first dinuclear metal‐mediated base pair containing divalent metal ions has been prepared. A combination of the neutral bis(monodentate) purine derivative 1,N6‐ethenoadenine (ϵA), which preferentially binds two metal ions with a parallel alignment of the N−M bonds, and the canonical nucleobase thymine (T), which readily deprotonates in the presence of HgII and thereby partially compensates the charge accumulation due to the two closely spaced divalent metal ions, yields the dinuclear T‐HgII2‐ϵA base pair. This metal‐mediated base pair stabilizes the DNA oligonucleotide duplex as shown by an increase of 8 °C in its melting temperature. Formation of the base pair was demonstrated by temperature‐dependent UV spectroscopy as well as by titration experiments monitored by UV and CD spectroscopy. 相似文献
167.
Sudhaker?UpadhyayEmail author Bhabani?Prasad?Mandal 《International Journal of Theoretical Physics》2016,55(1):1-7
Finite field-dependent BRST (FFBRST) transformations were constructed by integrating infinitesimal BRST transformation in a closed form. Such a generalized transformations have been extended in various branch of physics and found many applications. Recently BRST transformation has also been generalized with same goal and motivation in slightly different manner. In this work we have shown that the later formulation is conceptually equivalent to the earlier formulation. We justify our claim by producing the same result of later formulation using earlier FFBRST formulation. 相似文献
168.
169.
Using DFT calculations, this study investigates the pressure-dependent variations of elastic anisotropy in the following SnO2 phases: rutile-type (tetragonal; P42/mnm), CaCl2-type (orthorhombic; Pnnm)-, α-PbO2-type (orthorhombic; Pbcn)- and fluorite-type (cubic; Fm-3m). Experimentally, these polymorphs undergo sequential structural transitions from rutile-type → CaCl2-type → α-PbO2-type → fluorite-type with increasing pressure at 11.35, 14.69 and 58.22 GPa, respectively. We estimate the shear anisotropy (A1 and A3) on {1?0?0} and {0?0?1} crystallographic planes of the tetragonal phase and (A1, A2 and A3) on {1?0?0}, {0?1?0} and {0?0?1} crystallographic planes of the orthorhombic phases. The rutile-type phase shows strongest shear anisotropy on the {0?0?1} planes (A2 > 4.8), and the degree of anisotropy increases nonlinearly with pressure. In contrast, the anisotropy is almost absent on the {1?0?0} planes (ie A1 ~ 1) irrespective of the pressure. The CaCl2-type phase exhibits similar shear anisotropy behaviour preferentially on {0?0?1} (A3 > 5), while A1 and A2 remain close to 1. The α-PbO2-type phase shows strikingly different elastic anisotropy characterised by a reversal in anisotropy (A3 > 1 to < 1) with increasing pressure at a threshold value of 38 GPa. We provide electronic density of states and atomic configuration to account for this pressure-dependent reversal in shear anisotropy. Our study also analyses the directional Young’s moduli for the tetragonal and orthorhombic phases as a function of pressure. Finally, we estimate the band gaps of these four SnO2 phases as a function of pressure which are in agreement with the previous results. 相似文献
170.
A synthesis of an amphidinolides G and H C3-C18 subunits is reported. The C10-C18 segment 4 was prepared by a Negishi cross-coupling, whereas the synthesis of the C3-C9 fragment 5 employed an asymmetric cyanosilylation as the key step. The two segments were coupled by lithiation of iodide 4 and trapping of the anion with amide 5. The allylic epoxide moiety could be synthesized from the protected anti- mesylate 22. 相似文献