A novel one step synthesis of water soluble Au and Ag nanoparticles has been reported at room temperature using a naturally occurring bifunctional molecule, namely, gallic acid. The mechanistic details of nanoparticle formation were elucidated by carrying out control experiments using a variety of model compounds. The newly synthesized nanoparticles are extremely stable in the pH range of 4.5−5.0, due to (i) the strong electrostatic interaction of the carboxylate anion of the capping agent with the surface of the nanoparticle and (ii) a very high ζ potential (−45 mV). Under these pH conditions, it is difficult to bring nanoparticles in proximity due to strong interparticle electrostatic repulsion. However, the unique coordination behavior of Pb2+ ions (coordination number up to 12, flexible bond length and geometry) allows the formation of a stable supramolecular complex resulting in plasmon coupling and a visual color change. Because of the rigid coordination geometry, other metal cations (Ca2+, Cu2+, Cd2+, Hg2+, Mg2+, Ni2+, and Zn2+) interact only with lesser numbers of ligands, leaving the nanoparticles isolated; hence, no spectral change was observed under the experimental conditions. The ratiometric plots of the aggregated to the isolated forms indicate a high sensitivity as well as selectivity of Au and Ag nanoparticles toward Pb2+ ions. One of the significant features of the present system is its ability to detect micromolar quantities (ppm level) of Pb2+ ions in the presence of other metal cations in water. Further, we have theoretically modeled the interaction between the newly synthesized nanoparticles and the Pb2+ ion, and various optimized geometries are evaluated. On the basis of the experimental and theoretical studies, a tentative structure of the supramolecular complex leading to a strong interparticle interaction is provided.

Values of the molecular electrostatic potential minimum (V(min)) corresponding to the lone pair region of several substituted phosphine ligands (PR(3)) have been determined at the DFT level. The V(min) value is proposed as a quantitative measure of the electronic effect of the PR(3) ligands. Good linear correlation between V(min) and Tolman electronic parameter of PR(3) has been obtained. V(min) is also proportional to the pK(a) values of the conjugate acids of PR(3), viz., [PR(3)H](+). Further, the DeltaE values of the reaction Ni(CO)(3) + PR(3) --> Ni(CO)(3)PR(3) and ScH(3) + PR(3) --> ScH(3)PR(3) are also linearly proportional to the V(min) values. However, if there is a strong metal to phosphorus pi-back-bonding, the DeltaE and V(min) do not fit to a line. It is also found that the standard reduction potential as well as the enthalpy change corresponding to the electrochemical couple eta-Cp(CO)(PR(3))(COMe)Fe(+)/eta-Cp(CO)(PR(3))(COMe)Fe(0) is linearly proportional to the V(min) values of PR(3). These correlations suggest that V(min) is a quantitative measure of the sigma-donating ability of the phosphine. It is hoped that, in phosphine-metal coordination chemistry, the V(min) based electronic parameter could be more advantageous than nu-CO and pK(a) based electronic parameters as it solely represents the inherent electronic property of the ligand.

Hydrogen, halogen, and dihydrogen bonds in weak, medium and strong regimes (<1 to ∼ 60 kcal/mol) have been investigated for several intermolecular donor-acceptor (D-A) complexes at ab initio MP4//MP2 method coupled with atoms-in-molecules and molecular electrostatic potential (MESP) approaches. Electron density ρ at bond critical point correlates well with interaction energy (Enb) for each homogeneous sample of complexes, but its applicability to the entire set of complexes is not satisfactory. Analysis of MESP minimum (V(min)) and MESP at the nuclei (Vn) shows that in all D-A complexes, MESP of A becomes more negative and that of D becomes less negative suggesting donation of electrons from D to A leading to electron donor-acceptor (eDA) interaction between A and D. MESP based parameter ΔΔVn measures donor-acceptor strength of the eDA interactions as it shows a good linear correlation with Enb for all D-A complexes (R(2) = 0.976) except the strongly bound bridged structures. The bridged structures are classified as donor-acceptor-donor complexes. MESP provides a clear evidence for hydrogen, halogen, and dihydrogen bond formation and defines them as eDA interactions in which hydrogen acts as electron acceptor in hydrogen and dihydrogen bonds while halogen acts as electron acceptor in halogen bonds.

Full characterization of the molecular electrostatic potential (MESP) topography of the π-regions of 12 polycyclic benzenoid hydrocarbons (PBHs) is carried out. Benzene is endowed with the most perfect circular distribution of π-delocalization, and the hexagonal rings of other systems possess varying degrees of lesser π-delocalization. The topographical features describe Clar's aromatic sextet theory very well and simplify the aromatic characterization of each ring of a PBH system. The concepts such as “aromatic dilution” observed for polyacene series and the “empty ring” in triphenylene, perylene, and coronene are clearly brought out from this study. The positions of (3, +3) critical points (CPs) are always observed very close to shorter bonds, providing valuable hints at how the π-electrons are shared among the carbons. Further, average values of the MESP at CPs calculated for each ring ( ) and for the whole molecule ( ) bear linear correlation with the local aromaticity values estimated by Li and Jiang and the hardness values reported by Zhou and Parr for the global aromaticity, respectively. Thus the mapping of the MESP topography provides an elaborate characterization of the π-regions of PBH systems and a description of the intimately connected aromaticity.

The unique photophysical, conformational, and electronic properties of two model phenyleneethynylene-based rigid rod molecular systems, possessing dialkoxy substitutions, are reported in comparison with an unsubstituted system. Twisting of the phenyl rings along the carbon-carbon triple bond is almost frictionless in these systems giving rise to planar as well as several twisted ground-state conformations, and this results in broad structureless absorption in the spectral region of 250-450 nm. In the case of 1,4-bis(phenylethynyl)benzene, a broad absorption band was observed due to the HOMO-LUMO transition, whereas dialkoxy-substituted compounds possess two well-separated bands. Dialkoxy substitution in the 2,5-position of the phenyl ring in phenyleneethynylenes alters its central arene pi-orbitals through the resonance interaction with oxygen lone pairs resulting in similar orbital features for HOMO and HOMO-1/HOMO-2. Electronic transition from the low-lying HOMO-1/HOMO-2 orbital to LUMO results in the high-energy band, and the red-shifted band originates from the HOMO-LUMO transition. The first excited-state transition energies at different dihedral angles, calculated by the TDDFT method, indicate that the orthogonal conformation has the highest excitation energy with an energy difference of 15 kcal/mol higher than the low-lying planar conformation. The emission of these compounds originates preferentially from the more relaxed planar conformation resulting in well-defined vibronic features. The fluorescence spectral profile and lifetimes were found to be independent of excitation wavelengths, confirming the existence of a single emitting species.

Substituent effects in organic chemistry are generally described in terms of experimentally derived Hammett parameters whereas a convenient theoretical tool to study these effects in π-conjugated molecular systems is molecular electrostatic potential (MESP) analysis. The present study shows that the difference between MESP at the nucleus of the para carbon of substituted benzene and a carbon atom in benzene, designated as ΔVC, is very useful to quantify and classify substituent effects. On the basis of positive and negative ΔVC values, a broad classification of around 381 substituents into electron withdrawing and donating categories is made. Each category is again sorted based on the magnitude of ΔVC into subcategories such as very strong, strong, medium, and weak electron donating/withdrawing. Furthermore, the data are used to show the transferability and additivity of substituent effects in π-conjugated organic molecules such as condensed aromatic, olefinic, acetylenic, and heterocyclic systems. The transferability properties hold good for ΔVC in all these molecular systems. The additive properties of substituent effects are strongly reflected on ΔVC and the predictive power of the data to assign the total substituent effects of multi-substituted systems is verified. The ΔVC data and the present classification of substituents are very useful to design π-conjugated organic molecular systems with desired electron rich/poor character.

An adj-dicarbacorrole with CCNN in the core is achieved by replacing the bipyrrole moiety by a simple polycyclic aromatic hydrocarbon, such as biphenyl unit. Spectroscopic studies and structural analyzes confirm the absence of macrocyclic aromatization, thus leading to overall nonaromatic character. The trianionic core is effectively utilized to stabilize a copper(III) ion to form an organocopper complex.

A clear-cut definition of lone pairs has been offered in terms of characteristics of minima in molecular electrostatic potential (MESP). The largest eigenvalue and corresponding eigenvector of the Hessian at the minima are shown to distinguish lone pair regions from the other types of electron localization (such as π bonds). A comparative study of lone pairs as depicted by various other scalar fields such as the Laplacian of electron density and electron localization function is made. Further, an attempt has been made to generalize the definition of lone pairs to the case of cations.