4‐Amino derivatives of 7‐nitro‐2,1,3‐benzoxadiazole: the effect of the amino moiety on the structure of fluorophores

The crystal structures of three 4‐amino derivatives of 7‐nitro‐2,1,3‐benzoxa­diazole with increasing substituent ring size, viz. 7‐nitro‐4‐(pyrrolidin‐1‐yl)‐2,1,3‐benzoxa­diazole, C₁₀H₁₀N₄O₃, 7‐nitro‐4‐(piperidin‐1‐yl)‐2,1,3‐benzoxa­diazole, C₁₁H₁₂N₄O₃, and 4‐(azepan‐1‐yl)‐7‐nitro‐2,1,3‐benzoxa­diazole, C₁₂H₁₄N₄O₃, have been determined in order to understand their photophysical behaviour. All three were found to crystallize in centrosymmetric space groups. There is considerable electron delocalization compared with the parent compound, although the five‐membered oxa­diazole ring apparently does not participate in this. The length of the C—N bond between the amino N atom and the 7‐nitro­benzoxa­diazole system is found to be shorter than in similar compounds, as is the C—N_nitro bond. In each structure, the nitro group lies in the plane of the benzoxa­diazole unit.     

Synthesis of silver nanoparticle in imidazolium and pyrolidium based ionic liquid reverse micelles: A step forward in nanostructure inorganic material in room temperature ionic liquid field

Two silver salts, silver tetrafluoroborate and silver trifluoromethanesulfonate were dissolved in two different room temperature ionic liquids (RTILs), 1-Butyl-3 methyl imidazolium tetrafluoroborate ([Bmim][BF₄]) and 1-Butyl-1 methyl pyrrolidinium trifluoromethanesulfonate ([Bmpy][Tfms]). Triton x-100 (TX-100) surfactant and cyclohexane as nonpolar medium are used to dissolve these RTILs to create reverse micellar system. Pure reverse micellar system is characterized by dynamic light scattering (DLS) measurement. These pure RTIL reverse micellar systems are used to prepare stable silver nanoparticle solution without using any other auxiliary solvent in the whole process.     

Size tunable synthesis of cysteine-capped CdS nanoparticles by gamma-irradiation

Highly water soluble and biocompatible L-cysteine-capped CdS nanoparticles having narrow size distribution were synthesized for the first time by gamma-irradiation technique without using any additional stabilizer. FTIR study shows that CdS nanoparticles are capped through mercapto-group of cysteine amino acid while its free amino and carboxylate groups make it amenable to bio-conjugation. Size and luminescence of the nanoparticles can be well controlled by varying the parameters like radiation dose, pH and concentration of cysteine. The observed results suggest that pH 7 can be optimum for the synthesis of L-cysteine-capped CdS nanoparticles. CdS nanoparticles synthesized with molar ratio of Cd(2+):cysteine, 1:60 at pH 7 were found to be most luminescent. All nanoparticles formed lie in the size quantization regime and exhibit good crystallinity. Remarkable improvement in stability and luminescence was achieved on changing pH of as-prepared nanoparticles from 7 to 11.     

Size dependent interaction of biofunctionalized CdS nanoparticles with tyrosine at different pH

Enhancement of fluorescence of CdS nanoparticles by tyrosine at pH 10 in contrast to Stern-Volmer quenching at pH 7 was observed and both the effects were found to depend on the size of the nanoparticles.     

Ion effects in REDOX cycling of conducting polymer based electrochromic materials

Conducting polymer based electrochromic devices were assembled with various ionic liquid (IL) based electrolytes to probe the role of the ion structure on electrochromic performance. When the IL contained the same anion as the dopant ion used in the conducting polymers an enhanced electrochromic performance was observed providing high photopic contrast at low applied potential.     

Effect of water on the molecular structure and arrangement of nitrile-functionalized ionic liquids

Water changes the physical properties of ionic liquids (ILs). In this paper, the effect of water on ILs is investigated at the molecular level. The molecular structure and arrangement of 1-butyronitrile-3-methylimidazolium halide, in the presence and absence of the intruded water molecule, have been elucidated by single-crystal X-ray crystallography and near-infrared Raman spectroscopy. Water molecule is found to change the conformation of the n-butyronitrile chain of the cation. The hydrogen bonding interaction between the anion and water molecule, leading to loose molecular packing, is most likely to be responsible for the change. Distinct molecular structures and arrangements of ILs with and without water molecule have been presented here for the first time. As the unique properties of ILs are related to their structures and molecular arrangements, the presence of water, wanted or unwanted, must be carefully examined in any kind of IL research and applications.     

Synthesis, structure, UV-Vis-IR spectra, magnetism and theoretical studies on Cu[(2-aminomethyl)pyridine](thiocyanate)2 and comparisons with an analogous Cu complex

The title complex was synthesized under self-assembly conditions using Cu(acetate)₂·H₂O, 2-amp (= 2-aminomethylpyridine) and KSCN, and was characterized by IR, elemental analysis and single crystal structural analysis, and its spectral and RT magnetic properties were investigated. The asymmetric unit consists of a square planar Cu(II) center, with two ligand N atoms and two anionic Ns forming the square plane. In the unit cell, the monomeric complex assembles into 2-D layers through very weak non-bonded interactions between anionic S and Cu²⁺. Further, the structure was satisfactorily modeled by calculations based on Density Functional Theory (DFT), and the UV-Vis and IR spectra are analyzed in depth with the help of Time Dependent DFT (TDDFT). The results indicate that the absorption maxima are at relatively high energy and are mainly assigned to π → π^∗ transitions (in pyridine), with a fair contribution of metal to ligand charge transfer (MLCT) and ligand to ligand charge transfer (LLCT) transitions. All the low lying transitions are categorized as mixed MLCT/LLCT. A very weak but broad band in the higher wavelength region has been detected and identified as a d-d transition band. Also, it has been found that when the ligand ratio is modified, the formation of Cu(2-amp)₂(SCN)₂ takes place under the same self-assembly conditions, whose structure only has been recently reported. Structural, spectral and theoretical comparisons are presented for both complexes.     

Mössbauer study of Cd0.1Ni0.9Sn y Fe2−2y O4 ferrites

Mössbauer spectra of Cd_0.1Ni_0.9Sn_yFe_2?2yO₄ (y=0.0 to 0.5) ferrite system have been studied. The spectra suggest the existence of two hyperfine fields, one due to Fe³⁺ tetrahedral (A) site ions and the other due to Fe³⁺ octahedral (B) site ions. The variation of isomer shift, quadrupole interaction and internal magnetic fields of⁵⁷Fe³⁺ ions in both A and B sites have been determined as function of tin concentration. The systematic decrease in Curie temperature observed in the above system with tin concentration is explained on the basis of exchange interaction.     

Synthesis and study of the properties of stereocontrolled poly(N-isopropylacrylamide) gel and its linear homopolymer prepared in the presence of a Y(OTf)3 Lewis acid: effect of the composition of methanol-water mixtures as synthesis media

Poly(N-isopropylacrylamide) (PNIPAM) hydrogels and the corresponding linear homopolymers were synthesized in different methanol-water mixtures (x(m) = 0, 0.13, 0.21, 0.31, 0.43, 0.57, and 0.76, where x(m) is the mole fraction of methanol) in the presence of 0.1 M Y(OTf)(3) Lewis acid. The isotacticity (meso dyad (m), %) and cloud-point temperature of these homopolymers were gradually increased and decreased, respectively, with the increase in the x(m) values of the synthesis solvent mixtures. Moreover, the corresponding linear PNIPAM homopolymers prepared in the absence of Y(OTf)(3) showed an almost constant isotacticity of m = 45% and a cloud-point temperature of 33.0 °C. A SEM study revealed that the resulting hydrogels were highly porous except for the gels prepared at x(m) = 0 and 0.76. The swelling ratios of these hydrogels in water at different temperatures and in different methanol-water mixtures at 20 °C and the deswelling rate and the reswelling rate of these hydrogels were studied. All of these swelling results were compared with that of the corresponding gels prepared in the absence of a Lewis acid (Biswas, C. S.; Patel, V. K.; Vishwakarma, N. K.; Mishra, A. K.; Bhimireddi, R.; Rai, R.; Ray, B. J. Appl. Polym. Sci.2012, DOI: 10.1002/app.36318) and explained on the basis of the porosity of the gel, the state of aggregation and isotacticity of the PNIPAM chain segment, and the cononsolvency of the methanol-water mixture toward the PNIPAM chain segment.     

Heteroleptic dipyrrinato complexes containing 5-ferrocenyldipyrromethene and dithiocarbamates as coligands: selective chromogenic and redox probes

Six heteroleptic dipyrrinato complexes [Ni(fcdpm)(dedtc)] (1), [Ni(fcdpm)(dipdtc)] (2), [Ni(fcdpm)(dbdtc)] (3), [Pd(fcdpm)(dedtc)] (4), [Pd(fcdpm)(dipdtc)] (5), and [Pd(fcdpm)(dbdtc)] (6) (fcdpm = 5-ferrocenyldipyrromethene; dedtc = diethyldithiocarbamate; dipdtc = diisopropyldithiocarbamate; dbdtc = dibutyldithiocarbamate) have been synthesized and characterized by elemental analyses and spectral (ESI-MS, IR, (1)H, (13)C NMR, UV-vis) and electrochemical studies. Crystal structures of 1, 2, 4, and 5 have been authenticated by X-ray single-crystal analyses. Nickel-based complexes 1-3 display selective chromogenic and redox sensing for Hg(2+) and Pb(2+) ions, while palladium complexes 4-6 display selective chromogenic and redox sensing only for Hg(2+). Electronic absorption, ESI-MS, and electrochemical studies indicated that sensing arises from interaction between 1-3 and Hg(2+)/Pb(2+) through sulfur of the coordinated dithiocarbamates, while it arises from the pyrrolic nitrogen of fcdpm and dithiocarbamate sulfur from 4-6 and Hg(2+). Different modes of binding between Ni and Pd complexes have further been supported by theoretical studies. The receptor-cation binding constants (K(a)) and stoichiometry between probes and Hg(2+)/Pb(2+) have been estimated by the Benesi-Hildebrand method and Job's plot analysis. Detection limits for 1-3 toward Hg(2+)/Pb(2+) and 4-6 for Hg(2+) have been found to be reasonably high.