Hydrogen-Bonding Induced Alternate Stacking of Donor (D) and Acceptor (A) Chromophores and their Supramolecular Switching to Segregated States

This paper reports comprehensive studies on the mixed assembly of bis-(trialkoxybenzamide)-functionalized dialkoxynaphthalene (DAN) donors and naphthalene-diimide (NDI) acceptors due the cooperative effects of hydrogen bonding, charge-transfer (CT) interactions, and solvophobic effects. A series of DAN as well as NDI building blocks have been examined (wherein the relative distance between the two amide groups in a particular chromophore is the variable structural parameter) to understand the structure-dependent variation in mode of supramolecular assembly and morphology (organogel, reverse vesicle, etc.) of the self-assembled material. Interestingly, it was observed that when the amide functionalities are introduced to enhance the self-assembly propensity, the mode of co-assembly among the DAN and NDI chromophores no longer remained trivial and was dictated by a relatively stronger hydrogen-bonding interaction instead of a weak CT interaction. Consequently, in a highly non-polar solvent like methylcyclohexane (MCH), although kinetically controlled CT-gelation was initially noticed, within a few hours the system sacrificed the CT-interaction and switched over to the more stable self-sorted gel to maximize the gain in enthalpy from the hydrogen-bonding interaction. In contrast, in a relatively less non-polar solvent such as tetrachloroethylene (TCE), in which the strength of hydrogen bonding is inherently weak, the contribution of the CT interaction also had to be accounted for along with hydrogen bonding leading to a stable CT-state in the gel or solution phase. The stability and morphology of the CT complex and rate of supramolecular switching (from CT to segregated state) were found to be greatly influenced by subtle structural variation of the building blocks, solvent polarity, and the DAN/NDI ratio. For example, in a given D-A pair, by introducing just one methylene unit in the spacer segment of either of the building blocks a complete change in the mode of co-assembly (CT state or segregated state) and the morphology (1D fiber to 2D reverse vesicle) was observed. The role of solvent polarity, structural variation, and D/A ratio on the nature of co-assembly, morphology, and the unprecedented supramolecular-switching phenomenon have been studied by detail spectroscopic and microscopic experiments in a gel as well as in the solution state and are well supported by DFT calculations.     

Ion Interactions with a New Ditopic Naphthalimide‐Based Receptor: A Photophysical,NMR and Theoretical (DFT) Study

A new multi‐component chemosensor system comprising a naphthalimide moiety as fluorophore is designed and developed to investigate receptor–analyte binding interactions in the presence of metal and non‐metal ions. A dimethylamino moiety is utilized as receptor for metal ions and a thiourea receptor, having acidic protons, for binding anions. The system is characterized by conventional analytical methods. The absorption and fluorescence spectra of the system consist of a broad band typical for an intramolecular charge transfer (ICT). The effects of various metal‐ion additives on the spectral behavior of the present sensor system are examined in acetonitrile. It is found that among the metal ions studied, alkali/alkaline earth‐metal ions and transition‐metal ions modulate the absorption and fluorescence spectra of the system. As an additional feature, the anion signaling behavior of the system in acetonitrile is studied. A decrease in fluorescence efficiency of the system is observed upon addition of fluoride and acetate anions. Fluorescence quenching is most effective in the case of fluoride ions. This is attributed to the enhancement of the photoinduced electron transfer from the anion receptor to the fluorophore moiety. Hydrogen‐bond interactions between the acidic NH protons of the thiourea moiety and the F^? anions are primarily attributed to the fluoride‐selective signaling behavior. Interestingly, a negative cooperativity for the binding event is observed when the interactions of the system are studied in the presence of both Zn²⁺ and F^? ions. NMR spectroscopy and theoretical calculations are also carried out to better understand the receptor–analyte binding.     

One-pot synthesis of strong solid state emitting mono-cyclometalated iridium(III) complexes: study of their aggregation induced enhanced phosphorescence

Strong solid-state greenish-blue emitting, mono-cyclometalated iridium complexes, [Ir(ppy)(PPh(3))(2)(H)(Cl)], 2a and [Ir(F(2)ppy)(PPh(3))(2)(H)(Cl)], 2b [ppyH = 2-phenylpyridine; F(2)ppyH = 2-(2',4'-difluoro)phenylpyridine], have been synthesized by a convenient route. The 'aggregation induced enhanced phosphorescence (AIEP)' activity exhibited by these complexes has been rationalized.     

Singularity-free dark energy star

We propose a model for an anisotropic dark energy star where we assume that the radial pressure exerted on the system due to the presence of dark energy is proportional to the isotropic perfect fluid matter density. We discuss various physical features of our model and show that the model satisfies all the regularity conditions and is stable as well as singularity-free.     

Motion of test particles around global monopoles in Brans-Dicke theory

A detailed analysis of the motion of test particles around global monopole in Brans-Dicke theory of gravity has been prescribed using the Hamilton-Jacobi (H-J) formalism. The trajectory of the test particles are trapped by the monopole with some restriction on the coupling parameter ω.     

Galactic rotation curves inspired by a noncommutative-geometry background

This paper discusses the observed flat rotation curves of galaxies in the context of noncommutative geometry. The energy density of such a geometry is diffused throughout a region due to the uncertainty encoded in the coordinate commutator. This intrinsic property appears to be sufficient for producing stable circular orbits, as well as attractive gravity, without the need for dark matter.