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Alkali atom-doped hexalithioborazine (B3N3Li6-M) as a novel class of super-alkali complex has been investigated for their exceptionally high first-order and second-order electrical responsive properties. The stability of resulting complexes, B3N3Li6-M (M = Li, Na, and K), is confirmed by the ADMP simulation and the negative values of thermodynamic parameters such as binding energy (∆Eb) and Gibbs free energy (∆G). The relationship between aromaticity (NICS) and first hyperpolarizability of B3N3Li6-M follows linear relationship. Diffuse electron cloud around the central ring and doped alkali metal in the HOMO of B3N3Li6-M complexes has been attributed to the charge transfer from peripheral Li to the dopant metal (M) atom. The dipole moment of B3N3Li6-M varies between 0.507 D (M = Na) and 1.608 D (M = Li) due to charge transfer in these complexes. The mean polarizabilities (αav) of B3N3Li6-M ranging from 573.08 to 1598.86 a.u are observed. Exceptionally high value of second-order NLO parameter (βav = 5.133 × 105 a.u and βHRS = 2.166 × 106 a.u) are observed in case of Li-doped B3N3Li6 in this series. Thus, the first hyperpolarizability (βav and βHRS) values of the complexes produced by the interactions between alkali metal atoms (M) and B3N3Li6 are strong enough to demonstrate as potential second-order NLO materials. [ABSTRACT FROM AUTHOR]

A designed aggregation-induced emission enhancement (AIEE) active fluorescence probe 2,3-Bis-[(2-hydroxy-napthalen-1-ylmethylene)-amino]-but-2-enedinitrile (L) was synthesized via one step condensation method. The probe shows swift sensitivity and selectivity toward Al3+over other relevant metal ions and also exhibits significant AIEE phenomena in methanol/water mixture. Significant enhancement of fluorescence intensity is triggered via chelation-enhanced fluorescence through complex (Al3+-L) formation. A 2:1 metal to ligand ratio is observed from Job's plot based on UV − Vis absorption titration and detection limit (LOD) is found as low as 31.14 nM. Moreover, 1H NMR titrations and fluorescence reversibility by adding Al3+ and EDTA sequentially had been performed to establish the binding site of sensor complex (Al3+-L). Time-resolved photoluminescence, dynamic light scattering, optical microscopy, and on-site visualization studies have been performed to understand the AIEE mechanism of L in different volume percentage of water and methanol mixture. An INHIBIT molecular logic gate has been constructed utilizing the fluorescence behavior of the probe, L in presence of Al3+ and strong chelating ligand EDTA. [ABSTRACT FROM AUTHOR]

Context: Quantum mechanical calculations involving electron correlation, frequency dispersion, and solvent effects were carried out to examine the second-order nonlinear optical response of various acceptor, X (-CF3, -CN, -NO2) substituted in N,N-dimethylaniline (DMA) and julolidine(JLD). Here, both DMA and JLD acts as donor and the three substituted groups, X (-CF3, -CN and -NO2) at the para position of both the ring systems as acceptor. The NLO response (βHRS) of -CF3 and -CN substituted DMA and JLD is relatively lower compared to DMA-NO2 and JLD-NO2. The charge distribution is found higher in case of -NO2 substituted DMA and JLD (±443 and ±449) compared to their -CF3 or –CN substitution. Electronic characteristics such as UV-Vis absorption spectra, crucial excited state parameters and charge transfer contribution to βHRS have been used to explain the NLO parameter of DMA-X and JLD-X. Variation of the incident optical frequency of light shows fluctuation of βHRS value and highest values of βHRS are obtain at the λmax frequency of each compound. Solvent polarity variation study on βHRS shows that βHRS varies linearly with the Kirkwood-Onsagar dielectric factor (D). Methods: All computational studies have been carried out using density functional theory (DFT) based method. Since CAM-B3LYP based hybrid functional improves the asymptotic behavior of the exchange interaction by dividing into short-range and long-range components, first hyperpolarizability values in the present study were computed using DFT/ CAM-B3LYP/ 6-31G+(d,p) level of theory. [ABSTRACT FROM AUTHOR]

Fluorescent chemosensor, 3-(Anthracen-2-yliminomethyl)-benzene-1,2-diol (ANB) has been synthesized by one-step condensation of 2-aminoanthracene and 2,3-dihydroxybenzaldehyde and characterized using 1H-NMR, FT-IR and Mass spectroscopic techniques. The probe ANB was found to be an efficient 'turn-on' fluorescence chemosensor for the selective detection of Al3+ ion over other metal ions in an aqueous solution. The chemosensor exhibits ~ 27-fold enhancement of emission intensity in presence of Al3+ ion. Fluorescence quantum values for ANB and (Al3+-ANB)-complex are 0.004 and 0.097, respectively. In addition, the binding constant and the limit of detection were found to be 1.22 × 104 M−1 and 0.391 µM, respectively. The chemosensor ANB binds to Al3+ ions in 2:1 stoichiometric ratio which was supported by Job's plot, 1H-NMR titration and florescence titration. Fluorescence reversibility of the sensor complex was well established by adding EDTA in the same condition and a molecular INHIBIT logic gate was fabricated using this reversible nature of the sensor complex. Additionally, the chemosensor ANB shows a novel aggregation-induced enhanced emission phenomenon, where the aggregate hydrosol of ANB shows enhance emission intensity. [ABSTRACT FROM AUTHOR]

A multi responsive fluorescent probe, N',2-bis(E-4-(diethylamino)-2-hydroxybenzylidene)hydrazine-1-carbothiohydrazideV(H2L) has been synthesized through one step condensation method. Probe, H2L shows 'turn-on' dual sensing properties towards Cd2+ and H2AsO4− at two distinct wavelength. The probe (H2L) is spectroscopically characterized and the chemo-sensing mechanism has been demonstrated through 1H NMR, absorption, steady state and time resolved emission study. The most promising advantage of the probe is its application in the one-pot detection of Cd2+ (λem = 462 nm) and H2AsO4−(λem = 492 nm) where intense emission appears at two different wavelengths and the observed limit of detection (LOD) of H2L towards Cd2+ and H2AsO4− are 2.67 × 10–8 M and 5.14 × 10–6 M respectively. Further the 'turn-on' emission property of H2L towards Cd2+ is applied to construct INHIBIT logic gate. [ABSTRACT FROM AUTHOR]

A Fluorescent chemosensor based on pyrene scaffold, 5-diethylamino-2-(pyren-1-yliminomethyl)-phenol (PDS) is synthesized using condensation method. It displays novel aggregation-induced emission (AIE) phenomena in its aggregated/solid state. The AIE characteristic of PDS is studied in CH3CN/H2O mixtures at different volume percentage of water and morphology of the aggregated particles are investigated by DLS and optical fluorescence microscopic study. The probe is aggregated into ordered one-dimensional (1-D) rod like microcrystals and exhibit high efficiency of solid-state emission with green colour. By taking advantage of its interesting AIE feature, the aggregated hydrosol has been utilized as 'off–on' type fluorescence switching chemosensor with superb selectivity and sensitivity towards Cu2+ions and the limit of detection (LOD) was calculated as low as 6.3 µM. A high Stern–Volmer quenching constant was estimated to be 2.88 × 105 M−1. The proposed chemosensor with AIE feature reveals a prospective view for the on-site visual recognition of Cu2+ ions in fluorescent paper strips and the synthesized probe is also exploited to find out the concentration of Cu2+ions in real water samples. [ABSTRACT FROM AUTHOR]