4-Amino­phthalimide

The mol­ecules in the title compound (systematic name: 5-aminoisoindole-1,3-dione), C8H6N2O2, are packed through N—H⋯O inter­molecular hydrogen-bonding inter­actions. Two types of hydrogen bonds are observed: one, involving the imide group, forms mol­ecular chains along the c axis and another two, involving the amino group, connect the mol­ecular chains

Photophysical and density functional studies of the interaction of a flavone derivative with the halides

The synthesis, photophysical behavior, and anion-sensing ability of a fluorescent molecular system, N-(3-methoxy-4-oxo-2-phenyl-4H-chromen-7-yl)-benzamide (1H), designed and developed with a view to sensing fluoride ions, are reported. NMR and density functional studies on the system have been carried out to determine the nature of the interaction between 1H and X− (X = halogen atom) responsible for fluoride-induced dramatic changes in the absorption and emission properties of 1H. The color change of 1H, which can be observed by the naked eye, is found specific to fluoride ion; it is unaffected by the presence of a large excess of Cl−, Br−, and I−, thus rendering 1H as a selective fluoride ion sensor in micromolar concentration in the visible region. The changes in the fluorescence behavior of 1H, specifically, the formation of an additional long-wavelength emission band in the presence of fluoride ion, allow ratiometric fluorescence signaling of the fluoride ion as well. The results suggest that abstraction of the acidic proton of 1H by the F− leading to the formation of 1− is responsible for the spectral changes that allow signaling of the F−. Density functional calculations of the optimized geometrical parameters and charge densities of the 1H···halide complexes confirm the proton abstraction mechanism of the signaling of F−. Calculations of the transition energies of the 1H, 1−, and 1H···F− (hydrogen-bonded complex) show that only 1− is responsible for the long-wavelength absorption and emission band observed in the presence of F−

A highly selective 'off-on' fluorescence chemosensor for Cr(III)

An 'off-on' fluorescence chemosensor for the selective signalling of Cr(III) has been designed exploiting the guest-induced inhibition of the photoinduced electron transfer signalling mechanism. The system shows an approximately 17-fold Cr(III)-selective chelation-enhanced fluorescence response in tetrahydrofuran and the system is highly selective against the background of environmentally and biologically relevant metal ions

Picosecond Solvation Dynamics of Coumarin153 in Bis(1-methyl-1H-imidazol-3-ium-3-yl)dihydroborate Cation Containing Room Temperature Ionic Liquid and Ionic Liquid-DMF Mixtures

Abstract: Steady state and time-resolved fluorescence behavior of coumarin153(C153) in bis(1-methyl-1H-imidazol-3-ium-3-yl)dihydroborate cation containing room temperature ionic liquid and its mixture with dimethylformamide (DMF) has been investigated. Density functional calculations on the present ionic liquid have been carried out to have ground state structural information of this system. C-H···N and C-H···O hydrogen bonding interactions between cationic and anionic moiety of the present ionic liquid has been observed. Steady state absorption and emission spectral profiles of C153 are found not to be influenced by the polar cosolvent. Time-resolved fluorescence anisotropy experiments show that the rotational motion of the probe becomes faster in presence of DMF. During time dependent dynamic Stokes shift measurements in ionic liquid-DMF mixtures, the average solvation time is found to decrease with the addition of DMF to the ionic liquid. The decrease in both average solvation and rotational time of probe molecule upon gradual addition of polar organic co-solvent is attributed to the lowering of bulk viscosity of the medium

Excitation-wavelength-dependent fluorescence behavior of some dipolar molecules in room-temperature ionic liquids

The fluorescence behavior of several dipolar molecules has been studied in three room-temperature ionic liquids, namely, [BMIM][BF4], [EMIM][BF4], and [BMIM][PF6], as a function of the excitation wavelength. Although a large majority of these systems show normal fluorescence behavior with no excitation wavelength dependence, a few systems surprisingly exhibit fairly strong excitation-wavelength-dependent fluorescence behavior in these media. The excitation-wavelength-dependent shift of the fluorescence maximum is measured to be between 10 and 35 nm. The various fluorescence parameters of the systems have been carefully examined to determine the factors that contribute to this kind of behavior, generally not observed in conventional media. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited-state relaxation processes, viz., solvation and energy transfer, are responsible for the excitation-wavelength-dependent fluorescence behavior of some of the systems

Probing the Aggregation Behavior of Neat Imidazolium-Based Alkyl Sulfate (Alkyl = Ethyl, Butyl, Hexyl, and Octyl) Ionic Liquids through Time Resolved Florescence Anisotropy and NMR and Fluorescence Correlation Spectroscopy Study

Aggregation behavior of a series of neat 1-ethyl 3-methylimidazolium alkyl sulfate (alkyl = ethyl, butyl, hexyl, and octyl) ionic liquids has been investigated through combined time-resolved fluorescence spectroscopy, 1-D and 2-D NMR spectroscopy, and fluorescence correlation spectroscopy (FCS). Interestingly, experimentally measured rotational relaxation times (τ_<i>r</i>) for ethyl, butyl, hexyl and octyl systems are measured to be 2.25, 1.64, 1.36, and 1.32 times higher than the estimated (from Stokes–Einstein–Debye theory) values for the same respective systems. This indicates that the emitting species is not the monomeric imidazolium moiety rather an associated species, and volume of the rotating fluorescing species decreases even though the length of the alkyl moiety on the anions is increased. The shift in the ¹H proton signal as well as a change in the width of the same signal upon dilution of the neat ionic liquids indicates that ionic liquids exist in the aggregated form. Further investigation through the 2D-ROESY experiment shows that interaction between imidazolium and sulfate is relatively stronger in the ethyl system than that of the longer octyl system. FCS measurements independently show that the hydrodynamic volume decreases with an increase in the anion chain length. The NMR and FCS results are consistent with the findings of the fluorescence anisotropy study

Understanding the influence of ethylene glycol on the microscopic behavior of imidazolium-based monocationic and dicationic ionic liquid

In the present work, the influence of a molecular co-solvent, ethylene glycol (EG) on the microscopic behaviour of an imidazolium-based dicationic ionic liquid (DIL) is analysed by employing time-resolved fluorescence anisotropy (TRFA) and nuclear magnetic resonance (NMR) spectroscopic techniques. In order to have a clear understanding of the specific role of DIL, a mono-cationic ionic liquid (MIL) containing an alkyl side chain unit, same as the alkyl spacer chain length of DIL, has also been investigated. The rotational diffusion of two fluorescent probes 9-PA and R110 have been carried out in both neat MIL and DIL and their mixtures with various fractions of EG. The analysis of the results has demonstrated that, within the studied concentration range, the microstructure of MIL encompassing both polar and nonpolar domains gets disrupted as the mole fraction of EG increases. However, a similar investigation in DIL has revealed that the micro-structure of DIL gets affected slightly when similar proportions of EG are added to DIL. This behaviour of DIL is attributed to the enhanced rigidity of the DIL structure due to its folded structural arrangements. Furthermore, NMR studies have provided additional insights into the interactions between the components of ILs and the added solvent. It has been observed that EG can form strong hydrogen-bonding interactions with the imidazolium-ring and alkyl chain protons of MIL. However, such interaction has not been observed in DIL. Moreover, the translational diffusion coefficient (Dt) value for the cationic moiety of both MIL and DIL, measured through NMR, has depicted that in the presence of EG, the change in Dtvalue is much higher for MIL than that for DIL. Overall, the outcome of the combined fluorescence and NMR studies have pointed out that the behaviour of DIL and MIL in the presence of a co-solvent is very different from one another and thus the individual mixture (IL+solvent) can be used for various targeted industrial applications