Tandrima Chaudhuri

Design and development of a new pyrromethene dye with improved photostability and lasing efficiency: theoretical rationalization of photophysical and photochemical properties.

In an attempt to develop a photostable and efficient pyrromethene compound for use in liquid dye lasers, three congeners of the commercially available pyrromethene 567 (PM567) laser dye were synthesized and their photophysical properties, lasing efficiencies, and photochemical stabilities were studied. In general the presence of an aryl group at C-8 of the pyrromethene chromophore increased the photostability. One of the congeners possessing a C-8 trimethoxyphenyl moiety showed significantly improved lasing parameters than PM567. Compared to PM567, the photochemical stability of the new dye was 2-fold, while it showed an equivalent lasing efficiency to that of PM567 at a significantly lower concentration. The increased photostability of these new dye molecules could be explained by theoretical calculation on their capacity to generate singlet oxygen ((1)O(2)) and probability of reaction with (1)O(2). Our calculations were in agreement with the experimental results and indicated that a systematic design of new derivatives of pyrromethene chromophore might lead to improved laser dye molecules.

Photophysical properties of the 8-phenyl analogue of PM567: A theoretical rationalization

The absorption and emission spectroscopic investigations of the C-8-phenyl substituted analogue of the pyrromethene dye PM567 in various polar, non-polar as well as protic and aprotic solvents are reported. The solvatochromic shifts of the spectral bands were studied in a multitude of polar, non-polar and protic, aprotic solvents followed by a multilinear regression in which several solvent parameters were simultaneously analysed. Comparison of the experimental results with those obtained by gas phase ab initio computation with CIS, TD-HF and TD-DFT theories using 6-31G* basis set reveal an overestimation of the experimentally measured excitation parameters by all these theoretical models. However, the trends in the experimental results agree with those calculated theoretically.

Pseudo-Five-Component Domino Strategy for the Combinatorial Library Synthesis of [1,6] Naphthyridines—An On-Water Approach

This work features the base-promoted on-water synthesis of [1,6]-naphthyridines from methyl ketones, malononitrile and phenols or thiols. The reaction conditions were carefully tuned to drive the product selectivity from 3H-pyrroles to [1,6]-naphthyridines. The advantages of this method lie in its simplicity, cost effectiveness, and environmental friendliness, representing a new effort toward the on-water synthesis of [1,6]-naphthyridines without starting from a nitrogen-containing heterocycle and highlighting the versatility of the nitrile functional group.

Recognition of steric factor in external association of xanthenocrown-5 and bis-napthalenocrown-6 with bis(benzimidazolium)propane borontetrafluoride.

This is the first report of charge transfer band for crown-axel H-bonding interaction in acetonitrile medium. Monte Carlo simulation established external association of small cavity crown with BBIM-propane dication axels. Resonance energy, binding constant and ratiometric detection of association of xanthenocrown-5 (1) and bis-napthalenocrown-6 (2) with bis-(benzimidazolium)propane borontetrafluoride (3a-3d) in acetonitrile determined the effect of steric factor towards association.

Bodipy recognizes polyaromatic hydrocarbons via C–H⋯F type weak H-bonding

Polycyclic aromatic hydrocarbons (PAHs) demonstrated unusual weak C–H⋯F type H-bonding interaction with meso-substituted Bodipy dyes (1–3) in ethanol medium. Isosbestic absorptions and enhancement of emission of Bodipy were spectroscopically detected with three chosen PAHs (naphthalene, anthracene and phenanthrene). IR, 1H and 19F NMR, cyclic voltammetry, powder X-ray and Monte Carlo simulation of adducts confirmed interaction of PAHs via C–H⋯F type H-bonding with the chosen dyes.

The new threading system 2-benzyl-5,6-dimethyl-1H-benzo[d]imidazolium – dibenzo-24-crown-8: a model for Monte Carlo calculations incorporating an anion for the first time in threaded structures

A new [2]pseudorotaxane containing a benzimidazolium hydrogen-bonding station for a dibenzo-24-crown-8 (DB24C8) macrocycle is described. The structure of the [2]pseudorotaxane formed is established by 1H NMR spectroscopy, 2D NOESY and a Monte Carlo protocol (including an anion for the first time).

Solvent and Zn2+ Binding Effects on the Photo-physical Properties of (Dibenzoylmethanato)boron Difluoride

Absorption and emission spectroscopic studies of (dibenzoylmethanato)boron difluoride (1bf) in various polar and non-polar, protic and aprotic solvents are reported. The solvatochromic shifts of the spectral bands were examined in terms of solvent properties, including donor and acceptor numbers, followed by multilinear regression in which several solvent parameters were simultaneously analyzed. This π-conjugated positively charged system exhibits excellent solvatochromism. Variations in the electronic absorption spectral characteristics of 1bf were studied in solution in the presence of zinc perchlorate. Absorption spectral studies indicate stable complex formation between the zinc ion and 1bf in the ground state in aprotic dipolar benzonitrile rather than in protic polar solvent methanol. Zinc ion binding of 1bf was theoretically rationalized through frontier molecular orbital interaction.

Internal charge transfer based ratiometric interaction of anionic surfactant with calf thymus DNA bound cationic surfactant: Study I

Cetyl trimethyl ammonium bromide (CTAB) binds calf thymus (ct-) DNA like anionic biopolymers electrostatically and established equilibrium both in the ground as well as in excited state in aqueous medium at pH 7. Anionic sodium dodecyl sulfate (SDS) does not show even hydrophobic interaction with ct-DNA at low concentration. On contrary, SDS can establish well defined equilibrium with DNA bound CTAB in ground state where the same CTAB-DNA isosbestic point reappears. First report of internal charge transfer (ICT) based binding of CTAB with ct-DNA as well as ICT based interaction of anionic SDS with DNA bound CTAB that shows dynamic quenching contribution also. The reappearance of anodic peak and slight increase in cathodic peak current with increasing concentration (at lower range) of anionic SDS, possibly reflect the release of CTAB from DNA bound CTAB by SDS.

Charge transfer energies of the complexes of (dibenzoylmethanato)boron difluoride with indeno-pyridines and polynuclear aromatic hydrocarbons

Charge transfer complexes of electron deficient (dibenzoylmethanato)boron difluoride (DBMBF2) with polyaromatic hydrocarbons (A), as well as with highly electron rich indeno-pyridines (I) compounds in ethanol medium have been studied by electronic absorption spectroscopy. Absorption band due to a charge-transfer (CT) transitions are observed in the visible region. Utilizing the CT transition energy, the vertical electron affinities (EA(v)) of DBMBF2 in ethanol has been calculated. The value of EA(v) for DBMBF2 is found to be 2.28 eV, this is the first report of its electron affinity value. We have calculated the degrees of CT and transition dipole strengths of the DBMBF2/A and DBMBF2/I complexes. Along with both theoretically calculated and experimentally obtained vertical ionization potentials of the indeno-pyridine donors have been estimated for the first time. I show high degree of charge transfer along with high ground state stability similar to that of A. Thus indeno-pyridine (I) donors are also as good as aromatic hydrocarbons (A) for DBMBF2, having equivalent ionization potential like that of aromatic hydrocarbons.

Zinc ion–tetraphenylporphyrin interactions in the ground and excited states

In the present article, tetraphenylporphyrin a new ratiometric fluorescence sensitizer for zinc ion has been proposed. Electronic absorption, emission and (1)H NMR spectral characteristics of meso-tetraphenylporphyrin (TPP) have been studied in acetonitrile medium in the presence of zinc perchlorate. Absorption spectral studies indicate the formation of a new complex between zinc ion and the porphyrin moiety in the ground state as distinguished from the characteristics of metalo(zinc) porphyrin compound. The energy of maximum fluorescence of porphyrin shifts towards blue with the addition of Zn(ClO(4))(2). Steady state emission studies point to the existence of two emitting species viz, the solvated and the complexed porphyrin in equilibrium. The fluorescence emission of tetraphenylporphyrin at 651-nm bands decreases while that at 605 nm increases upon zinc ion interaction in acetonitrile. Thus, the TPP can behave as a ratiometric fluorescent sensor. This fluorescence modulation of TPP should be applicable to dual-wavelength measurement of various biomolecules or enzyme activities. (1)H NMR spectra of the porphyrin suffered a radical change with the addition of zinc perchlorate which points to the formation of a new porphyrin complex. This change is due to the difference in the electron-donating ability of the pyrrolic nitrogens before and after complexation with Zn(2+). The values of equilibrium constant for the binding process have been determined in acetone and acetonitrile, in both ground and excited states.