K. Sankaran

Fluorescence and co-fluorescence of Tb3+ and Eu3+ in acetonitrile using 2,6-pyridine dicarboxylic acid as ligand

Fluorescence from Tb(3+) and Eu(3+) complexed with 2,6-pyridine dicarboxylic acid (PDA) has been studied using acetonitrile (MeCN) as solvent. The enhancement in fluorescence intensity because of non-aqueous environment provided by the MeCN is less significant, where as fluorescence enhancement of more than two orders of magnitude has been observed with the addition of La(3+); a process known as co-fluorescence in MeCN. The present study demonstrates for the first time co-fluorescence of Tb(3+) and Eu(3+) with excitation through the absorption of PDA. Intermolecular energy transfer is believed to be responsible for co-fluorescence enhancement and it becomes possible as the quenching due to water at the secondary coordination spheres of Tb(3+) and Eu(3+) is reduced when MeCN is used as solvent.

Ligand sensitized luminescence of uranyl by benzoic acid in acetonitrile medium: a new luminescent uranyl benzoate specie.

Benzoic acid (BA) is shown to sensitize and enhance the luminescence of uranyl ion in acetonitrile medium. Luminescence spectra and especially UV-Vis spectroscopy studies reveal the formation of tri benzoate complex of uranyl i.e. [UO2(C6H5COO)3](-) which is highly luminescent. In particular, three sharp bands at 431, 443, 461nm of absorption spectra provides evidence for tri benzoate specie of uranyl in acetonitrile medium. The luminescence lifetime of uranyl in this complex is 68μs which is much more compared to the lifetime of uncomplexed uranyl (20μs) in acetonitrile medium. In contrary to aqueous medium where uranyl benzoate forms 1:1 and 1:2 species, spectroscopic data reveal formation of 1:3 complex in acetonitrile medium. Addition of water to acetonitrile results in decrease of luminescence intensity of this specie and the luminescence features implode at 20% (v/v) of water content. For the first time, to the best of our knowledge, the existence of [UO2(C6H5COO)3](-) specie in acetonitrile is reported. Mechanism of luminescence enhancement is discussed.

Uranyl tris nitrato as a luminescent probe for trace water detection in acetonitrile

Uranyl tris nitrato i.e. [UO2 (NO3 )3 ]- was formed by adding tetramethylammonium nitrate to uranyl nitrate in acetonitrile medium. The luminescence features of this complex in acetonitrile are very sensitive to water content, which could lead to the use of it as a luminescent probe for water present in acetonitrile. The luminescence intensity ratio of 507 to 467xa0nm peak of uranyl tris nitrato showed a linear response in the range 0-5% (v/v) water content in acetonitrile. The present method was applied for three synthetic samples of acetonitrile for water detection and the results obtained were compared using Karl Fischer titration. There was a good agreement in the values obtained by both the methods.

Feasibility study for quantification of lanthanides in LiF–KCl salt by laser induced breakdown spectroscopy

Quantitative analysis of Pr, Nd, Ce, La and Sm were carried out simultaneously in LiF–KCl matrix using laser induced breakdown spectroscopic technique. Two non-interfering analytical emission lines have been identified for each lanthanide and using the internal standard method, the calibration curve is constructed from 0.3 to 5% for Pr, Nd, Ce and La and from 0.3 to 3% for Sm. Both the emission lines showed good regression coefficient (R2) ranging from 0.9953 to 0.9996. The analytical capability of this method is studied through the correlation uncertainty of measured values with its known value in synthetic samples containing all the lanthanides in equal amount (0.5, 1 and 2%). Low value of correlation uncertainty (less than 10%) confirms that LIBS has a great potential for quantitative analysis of lanthanides in LiF–KCl matrix.

Nitrogen: A New Class of π-Bonding Partner in Hetero π-Stacking Interaction

Spectroscopy under isolated conditions at low temperatures is an excellent tool to characterize the aggregates stabilized through weak interactions. Within the framework of weak interactions, the π-stacking interactions are considered unconventional with the limited experimental proofs, wherein the bonding associates are either aromatic and heterocyclic compounds or their combinations. Besides aromatic compounds, π-stacking networks can even be realized with molecules possessing electron rich π-clouds. In this work, the N2 molecule as a possible π-bonding partner is explored for the first time in which hetero π-stacking was achieved between pyrrole and N2 precursors. The matrix isolation experiments performed by seeding pyrrole and N2 mixtures in an Ar matrix at low temperatures with subsequent infrared spectral characterization revealed the generation of adducts stabilized through a π(pyrrole)···π(N2) interaction. Under identical conditions with the likelihood of two competing π-stacking and hydrogen-bonding interactions in pyrrole-N2 associates, π-stacking dominates energetically over hydrogen-bonding interaction.

Conformations of n-butyl imidazole: Matrix isolation infrared and DFT studies

Conformations of n-butyl imidazole (B-IMID) were studied using matrix isolation infrared spectroscopy by trapping in argon, xenon and nitrogen matrixes using an effusive nozzle source. The experimental studies were supported by DFT computations performed at the B3LYP/6-311++G(d,p) level. Computations identified nine unique minima for B-IMID, corresponding to conformers with tg(±)tt, tg(±)g(∓)t, tg(±)g(±)t, tg(±)tg(±), tg(±)tg(∓), tg(±)g(∓)g(∓), tg(±)g(±)g(±), tg(±)g(∓)g(±) and tg(±)g(±)g(∓) structures, given in order of increasing energy. Computations of the transition state structures connecting the higher energy conformers to the global minimum, tg(±)tt structure were carried out. The barriers for the conformer inter-conversion were found to be ∼2 kcal/mol. Natural Bond Orbital (NBO) analysis was performed to understand the reasons for conformational preferences in B-IMID.

Luminescent versus non-luminescent uranyl–picolinate complexes

Luminescence of uranyl ion (UO22+) complexed with picolinate (PA) has been studied in aqueous and acetonitrile medium. In aqueous medium, for UO22+ to PA ratio of up to 1:20, a 1:1 non-luminescent specie with stability constant of log βu2009=u20093.88 was formed. On the contrary, formed specie in acetonitrile medium was luminescent and the enhanced luminescence was due to sensitization by PA and reduction in non-radiative decay channels. UV–Vis absorption spectroscopy studies revealed that the luminescent specie was 1:2 type complex. Density functional theory and DLPNO-CCSD(T) methodologies were applied to arrive at the lowest-energy structures of the 1:1 and 1:2 uranyl–picolinate complexes.

The Influence of Branching on the Conformational Space: A Case Study of Tri-secondary-Butyl Phosphate Using Matrix Isolation Infrared Spectroscopy and DFT Computations

The conformational analysis of long chain phosphates poses a serious challenge due to the presence of rotationally flexible multiple alkyl groups. Tri- sec-butyl phosphate (TsBP) is an interesting example, in which branching can be expected to influence the conformational landscape. To solve the conformational problem of TsBP systematically, the conformations of model dimethyl- sec-butyl phosphate (DMsBP), a molecule possessing a single secondary butyl strand, were analyzed. On the basis of the analysis of the energy profile of DMsBP, a few conformational bunches were eliminated. The presence of branched methyl group appears to completely influence the conformational space of TsBP and as a result, the number of conformations is drastically reduced in comparison to its structural isomer, tri- n-butyl phosphate (TBP). B3LYP level of theory in association with 6-311++G(d,p) basis set was used for computing all the conformer geometries. Experimentally, the conformations of TsBP were studied using infrared spectroscopy by trapping the molecule in N2 and Ar matrixes at low temperatures, which were correlated well with the computational results.

Photooxidation of Trimethyl Phosphite in Nitrogen, Oxygen, and para-Hydrogen Matrixes at Low Temperatures

Trimethyl phosphite (TMPhite) was photooxidized to trimethyl phosphate (TMP) in N2, O2, and para-H2 matrixes at low temperatures to correlate the conformational landscape of these two molecules. The photooxidation produced the trans (TGG)-rich conformer with respect to the ground state gauche (GGG) conformer of TMP in N2 and O2 matrixes, which has diverged from the conformational composition of freshly deposited pure TMP in the low-temperature matrixes. The enrichment of the trans conformer in preference to the gauche conformer of TMP during photooxidation is due to the TMPhite precursor, which exists exclusively in the trans conformer. Interestingly, whereas the photooxidized TMP molecule suffers site effects possibly due to the local asymmetry in N2 and O2 matrixes, in the para-H2 matrix owing to the quantum crystal nature the site effects were observed to be self-repaired.