The absence of d-orbital electrons or presence of full-filled d-orbital electrons in metal ions is a well-known Achilles' heel problem for the detection of these metal ions by a simple UV-visible study. For this reason, detection of metal ions such as Al 3+ with no d-orbital electrons or Zn 2+ with filled d-orbital electrons is a challenging task. Herein, we report a 2-naphthol-based fluorescent probe [1-((E)-((E)-(5-bromo-2-hydroxybenzylidene)hydrazono)methyl)naphthalen-2-ol] (H 2 L) that has been used to sense and discriminate Al 3+ and Zn 2+ via solvent regulation. The probe exhibits excellent selectivity and swift sensitivity toward Al 3+ in MeOH− water (9:1, v/v) and toward Zn 2+ in dimethyl sulfoxide (DMSO)−water (9:1, v/v) among various metal ions. The respective detection limit is found to be 9.78 and 3.65 μM. The sensing mechanism is attributed to multiple processes, viz., the inhibition of photo-induced electron transfer (PET) along with the introduction of chelation-enhanced emission (CHEF) and excited-state intramolecular proton transfer (ESIPT) inhibition, which are experimentally well verified by UV−vis absorption spectroscopy, emission spectroscopy, and NMR spectroscopy. The probe shows aggregation-induced emissive (AIE) response in ≥70% aqueous media as well as in the solid state. The experimental results are well corroborated by time-resolved photoluminescence (TRPL) and density functional theory (DFT) calculations. An advanced-level OR-AND-NOT logic gate has been constructed from a different chemical combinational input and emission output. The reversible recognition of both Al 3+ in MeOH−water (9:1, v/v) and Zn 2+ in DMSO−water (9:1, v/v) is also ascertained in the presence of Na 2 EDTA, enabling the construction of a molecular memory device. The probe H 2 L also detects intracellular Al 3+ /Zn 2+ ions in Hela cells. Altogether, our fundamental findings will pave the way for designing and synthesis of unique chemosensors that could be used for cell imaging studies as well as constructing molecular logic gates.
The generation and study of metal-hydroperoxo/metal-peroxo (LCu(II)-OOH or LCu(II)-OO˙) complexes is a fascinating area of research of many chemical and biochemical researchers, because of their involvement as active intermediates in many biological and industrial catalytic oxidation processes. For this purpose we have designed a bulky hexa-coordinating ligand with potential N4O2 donor atoms which could provide an opportunity to synthesize a mononuclear Cu(II) complex with an aim to utilize it in the catalytic oxidation of aromatic hydrocarbons by an environmentally benign oxidant, H2O2. The Cu(II) complex (1) was structurally characterized and found to have square-planar geometry with the two pyrazolyl groups remaining in dangling mode. A novel mononuclear complex [Et3NH][LCu(II)-OOH] (2) was found to form in the reaction between 1 and H2O2 in the presence of Et3N. The presence of this dangling groups favours the stability of hydroperoxo species, [LCu-OOH](-) (2) through H-bonding with the coordinated phenoxo oxygen atom, which was confirmed by ESI-MS(+) and MS(-) (m/z) mass analysis and DFT calculations. This complex was found to be thermally stable at room temperature [k(d) = (5.67 ± 0.03) × 10(-5) s(-1) at 25 °C] and may be due to the formation of O-O-H···O(phenoxo) H-bonding as delineated by the DFT calculations. Complex 1 was found to be an efficient catalyst for the oxidation of aromatic hydrocarbons to the corresponding aldehyde and alcohol in 2:1 mole ratio with TON ~300.
A number of new amidooxime based manganese(II) complexes have been synthesized and characterized by single crystal X‐ray diffraction studies as well as by geometry optimization of complex 2 using DFT/B3LYP. All four complexes (1‐4) are mononuclear having octahedral geometry. DNA binding interaction and nuclease activity of these compounds were investigated for diverse biomedical applications. The results of photophysical studies indicated that the Mn(II) compounds bind with DNA by intercalation mode and the complex 1 containing pyrimidine moiety and chloro ligation showed highest binding affinity. The binding affinities of these compounds were of the order of 104‐105 M−1 and all of them were found to be capable of inducing DNA cleavage.
Two dinuclear Schiff-base complexes [Cu(II)Dy(III)] and [Co(III)Dy(III)] have been synthesized and structurally characterized. The AC susceptibility measurements taken at BDC = 0.2 T show a slow magnetic relaxation typical for single-molecule magnets. Unusual is the presence of three relaxation branches in [Cu(II)Dy(III)]; the slowest (low-frequency) process possesses the barrier to spin reversal of U/kB = 2.8 K and an extrapolated relaxation time as slow as τ0 = 0.11 s. The intermediate-frequency process is typical for SMM of this class with U/kB = 122 K and τ0 = 9.9 × 10(-7) s; an onset of the high-frequency process is evidenced and this is the fastest. In contrast, the [Co(III)Dy(III)] complex free of exchange coupling exhibits only a single relaxation path with SMM parameters U/kB = 113 K and τ0 = 7.0 × 10(-9) s.
A highly selective and sensitive fluorescent Zn(2+) sensor, 2,6-bis(2-hydroxy-benzoic acid hydrazide)-4-methylphenol (1), was designed and synthesized. In aqueous THF (4 : 6 v/v) ligand 1 induces a 2 : 1 complex formation with respect to Zn(2+) at physiological pH. This probe features visible light excitation(390 nm) and emission (490 nm) profiles, excellent selectivity responses for Zn(2+)over other competing biological metal ions with K(d) < 1 pM(2), LOD < 1 ng L(-1) and about 680 fold enhancement in fluorescent intensity upon Zn(2+) binding. It also exhibits cell permeability and intracellular Zn(2+) sensing in A375 human melanoma cancer cell.
A new rhodamine-based dual signaling probe (L 3 ) has been found to display quick responses through visible colorimetric changes as well as fluorogenic properties on selective 1:1 binding to Hg 2+ , as delineated by absorption and fluorescence titrations as well as by JobЈs method and ESI-MS + studies. The fluorescent probe L 3 displays a 252-fold fluorescence enhancement on binding to Hg 2+ . A Benesi-Hilderband fit of the absorption titration data gives K d = (32.01 Ϯ 0.74) μM and a 1:1 binding stoichiometry. Owing to
Both rhodamine and azobenzene moieties have been conjugated to prepare a novel chemosensor for the detection of Al3+ through CHEF-PET and the spirolactam ring opening mechanism.
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