Spectroscopic Rationalization of Selective Colorimetric Chemosensing of Fe(lll) in Aqueous Medium by a New Mono-Substituted Dibenzodiaza-Crown Ether Macrocyclic Ligand Appended with Mono 2-Benzimidazole N-Pendant Side Arm.

Optical chemosensor L comprising of a new mono-N-substituted derivative of dibenzodiaza-crown ether macrocyclic ligand bearing a 2-benzimidazole (2Bim) side arm was synthesized, and characterized by FT-IR, elemental microanalyses, 1H NMR, and 13C NMR, UV-visible, fluorescence (FL) spectroscopy. The colorimetric chemosensing behavior of L toward the library metal ions was examined, wherein L represented a prompt and selective yellow-to-purple color change for Fe(III) cation in a 25µM solution with LOD as 0.23 µM in ethanol:water (9:1, v/v), even in the presence of the other library metal ions (LMI). Based on the 1H NMR, UV-visible, and FL observations the coordination sphere of Fe(III) was shared with two 2-benzoimidazole (2Bim) side arms which were also confirmed by the elemental microanalyses (in the solid state) and the Job plot method (in the solution) of the complex. Moreover, the above-mentioned color change was attributed to the presence of a strong charge transfer (LMCT) band for the Fe(III)/L interaction in the solution. Furthermore, the viscosity measurement in the presence of Fe(III) uncovered an increase at 0.5-1.0 ratios for Fe(III)/L, attributable to the formation of a self-assembly in the solution. A TLC paper strip was impregnated by L for selective detection of Fe(III), demonstrating a live color change for Fe(III) at 0-5 mM in the presence of LMI.

Selective Supramolecular Recognition of Nitroaromatics by a Fluorescent Metal-Organic Cage Based on a Pyridine-Decorated Dibenzodiaza-Crown Macrocyclic Co(II) Complex.

Two isomorphous fluorescent (FL) lantern-shaped metal-organic cages 1 and 2 were prepared by coordination-directed self-assembly of Co(II) centers with a new aza-crown macrocyclic ligand bearing pyridine pendant arms (Lpy). The cage structures were determined using single-crystal X-ray diffraction analysis, thermogravimetric, elemental microanalysis, FT-IR spectroscopy, and powder X-ray diffraction. The crystal structures of 1 and 2 show that anions (Cl- in 1 and Br- in 2) are encapsulated within the cage cavity. 1 and 2 bear two coordinated water molecules that are directed inside the cages, surrounded by the eight pyridine rings at the "bottom" and the "roof" of the cage. These hydrogen bond donors, π systems, and the cationic nature of the cages enable 1 and 2 to encapsulate the anions. FL experiments revealed that 1 could detect nitroaromatic compounds by exhibiting selective and sensitive fluorescence quenching toward p-nitroaniline (PNA), recommending a limit of detection of 4.24 ppm. Moreover, the addition of 50 µL of PNA and o-nitrophenol to the ethanolic suspension of 1 led to a significant large FL red shift, namely, 87 and 24 nm, respectively, which were significantly higher than the corresponding values observed in the presence of other nitroaromatic compounds. The titration of the ethanolic suspension of 1, with various concentrations of PNA (>12 µM) demonstrated a concentration-dependent emission red shift. Hence, the efficient FL quenching of 1 was capable of distinguishing the dinitrobenzene isomers. Meanwhile, the observed red shift (10 nm) and quenching of this emission band under the influence of a trace amount of o- and p-nitrophenol isomers also showed that 1 could discriminate between o- and p-nitrophenol. Replacement of the chlorido with a bromido ligand in 1 generated cage 2 which was a more electron-donating cage than 1. The FL experiments showed that 2 was partially more sensitive and less selective toward NACs than 1.

Computational elucidation of the aging time effect on zeolite synthesis selectivity in the presence of water and diquaternary ammonium iodide.

An example of zeolite selectivity (MFI → MOR) driven by synthesis aging time has been studied. Using N,N,N',N'-tetramethyl-N,N'-dipropyl-ethylenediammonium diiodide (TMDP) as an organic structure-directing agent (OSDA), the zeolite phases obtained at 2 h (MFI 97%), 8 h (MFI 84%, MOR 16%) and 24 h (MFI 43%, MOR 57%) have been characterized by powder X-ray diffraction. The results suggest that at intermediate aging time, namely 8 h and 24 h, the dominant phase (MFI) is displaced by MOR. Different techniques (FT-IR, Raman, 13C MAS NMR, TGA/DTG and HC microanalysis) have been employed to verify the OSDA integrity and occlusion inside the zeolite micropores as well as to quantify the water and OSDA loading. The 1H MAS NMR of the as-made occluded zeolite was compared with the spectra of TMDP and the recovered OSDA from the sample by extraction with water. The comparison indicated that TMDP was not structurally intact, indicating the chemical transformation of TMDP to imidazolinium homologues through the Hofmann degradation process. Furthermore, careful acidic breakdown of the aluminosilicate shell, covered on the zeolite samples by hydrofluoric acid, revealed that the remaining OSDA had been partially degraded to lower molecular weight ammonium salt, confirmed by 1H NMR and mass spectrometry measurements. A computational study was performed by using a force field based methodology, including accurate loading of water and OSDA in the zeolite (MFI and MOR) unit cells. The results show an important contribution of the presence of water. The samples with larger aging time (8 h and 24 h) incorporate less water and show partial TMDP degradation, whilst at the shortest aging time (2 h), there is a larger water content and TMDP remains intact. The larger accessible volume of MFI justifies that this is the dominant phase at short aging times (large water content) since it can accommodate a larger number of water molecules than MOR. The OSDA partial degradation also plays a role. At longer aging times the partial OSDA decomposition has been considered in the models by including TMDP + Imidaz, which is more stabilized by MOR, whilst at shorter aging times the only OSDA present, TMDP, is better stabilized by MFI.

High-Impact Promotional Effect of Mo Impregnation on Aluminum-Rich and Alkali-Treated Hierarchical Zeolite Catalysts on Methanol Aromatization.

A systematic change of HZSM-5 (HZ5) as a catalyst of the methanol to aromatics (MTA) reaction was undertaken by employing a fixed-bed tubular-type reactor under ambient pressure, applying a weight hourly space velocity (WHSV) of 2 h-1 at 375 °C, as the first report on the application of low-Si/Al-ratio alkaline-[Mo,Na]-HZSM-5 in the MTA process. To characterize the surface and textural properties of the catalysts, powder X-ray diffraction (PXRD), nitrogen adsorption/desorption, temperature-programmed desorption of ammonia (NH3-TPD), pyridine-infrared spectroscopy (Py-IR), thermogravimetric analysis (TGA), and energy-dispersive X-ray (EDX) methods were employed. Gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) measurements demonstrated a selectivity of up to 86 wt % (65.7 wt % for benzene, toluene, and xylene (BTX)) over 2[Mo]HZ5. NH3-TPD and Py-IR results indicated a sensible decrease of strong acid sites on the impregnated samples, while the surface analyses revealed the highest Lewis acid sites (LAS) together with the largest mesopore surface area for 2[Mo]alk-HZ5, supporting the migration of Mo species to the bulk of the catalysts. Mo impregnation had a minor effect on the observed coke formation in the promoted catalyst.

Highly Efficient Production of Benzene-Free Aromatics from Methanol over Low-Si/Al-Ratio Alkali-Modified Fe/Zn/HZSM-5.

Herein, the methanol conversion to aromatic hydrocarbons was studied over a new family of mesoporous low-silica HZSM-5 (Si/Al = 11) catalysts in a fixed-bed tubular reactor under ambient pressure at 375 °C, feeding with weight hourly space velocity of 2 h-1. The catalysts were prepared in the absence and presence of Zn and Fe in both alkaline and neutral aqueous solutions, characterized by using X-ray diffraction, X-ray fluorescence, temperature programmed desorption of ammonia, N2 adsorption/desorption, thermogravimetric analysis, Fourier-transform infrared, transmission electron microscopy (TEM), field emission scanning electron microscopy and FE-SEM/energy dispersive X-ray spectroscopy techniques. The [0.2Fe,0.3Zn]-alk-HZSM-5 catalyst exhibited novel selectivity for aromatics (>86 wt %), specifically for m and p-xylenes (44.7 wt %) alongside 0.1 wt % for benzene.

A Unique Sensitive and Highly Selective Fluorescent Naphthodiaza-Crown Macrocyclic Ligand Chemosensor for Hg2+ in Water.

The noticeable enhancement in fluorescence emission of O2N2-donor naphthodiaza-crown macrocyclic ligand (L) in the presence of Hg2+ was observed in which the fluorescence quantum yield of free ligand L as well as L/Hg2+ complex were found to be as 0.29 and 0.49, respectively. The observed ultra-low limit of detection (LOD) for Hg2+ by L was determined as low as 1.0 × 10-11 M in water. A 1:1 stoichiometry was also established for L/Hg2+ together with a binding constant K BH = 66,543 by employing fluorescence spectrophotometry. The competition experiments on L/Hg2+ demonstrated highly selective detection of Hg2+ in the presence of the library cations. A two path mechanism for detection of metal ion in terms of coordination of metal ion to L and/or the formation of counter ion was proposed by using of 1H NMR and fluorescence spectroscopy. Graphical Abstract pH dependence mechanism of interaction between Hg2+ and macrocyclic ligand L.

Through-space electronic communication of zinc phthalocyanine with substituted [60]Fullerene bearing O2Nxaza-crown macrocyclic ligands.

Two new macrocyclic ligands containing 17- and 19-membered O2N3-donor aza-crowns anchored to [60]Fullerene were synthesized and characterized by employing HPLC, electrospray ionization mass (ESI-MS), 1H and 13C NMR, UV-vis, IR spectroscopies, as well as powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA) in solid state. TGA measurements revealed that upon linking each of these macrocycle rings to [60]Fullerene, the decomposition point measured for [60]Fullerene moiety was increased, indicating on the promoted stability of [60]Fullerene backbone during binding to these macrocyclic ligands. Moreover, the ground state non-covalent interactions of [60]Fullerene derivatives of O2Nx (x=2, and 3) aza-crown macrocyclic ligands namely, L1-L4 with zinc phthalocyanine (ZnPc) were also investigated by UV-vis absorption, steady state and time resolved fluorescence spectrophotometry in N-methyl-2-pyrrolidone (NMP). The calculation of Stern-Volmer constants (KSV) indicated on existence of an efficient quenching mechanism comprising of the excited singlet state of ZnPc in the presence of L1-L4. The observation of an appropriate correlation between decrease in fluorescence intensity and lifetime parameters led us to propose the occurrence of a static mechanism for the fluorescence quenching of ZnPc in the presence of L1-L3. The binding constants (KBH) of L1-L4/ZnPc were also determined applying the fluorescence quenching experiments. Meanwhile, the incompatibility of both KSV and KBH values found for L4 was also described in terms of structural features using DFT calculations using the B3LYP functional and 6-31G* basis set.

Spectroscopic evidence on improvement in complex formation of O2N2 aza-crown macrocyclic ligands with Cu(II) acetate upon incorporation with [60]Fullerene.

The present paper reports the spectroscopic investigations on the complexation of Cu(II) with two macrocyclic ligands bonded to [60]Fullerene (L1 and L2) measured in N-methylpyrrolidone (NMP) as solvent. On the basis of UV-vis-NIR spectroscopy applying Jobs method of continuous variation, typical 1:1 stoichiometries were established for the complexes of Cu(II) with L1, and L2. DFT calculations suggested that superior HOMO distributions spread over the nitrogen-donor (as well as somehow oxygen- donor in L2) groups of L1 and L2 macrocycles were the key factor for the observed Kb value enhancement. Thermodynamic stabilities for these complexes have also been determined employing Benesi-Hildebrand equation and the results were compared in terms of their calculated binding constants (Kb). These measurements showed that L1 and L2 bound to these cations stronger than their parent free macrocyclic ligands 1 and 2, respectively. Furthermore, Kb values found for L2 complexes revealed that it could coordinate Cu(II) cation better than L1. Thermodynamic parameters (ΔG, ∆H, and -ΔS) derived from Van't Hoff equation showed that L1 and L2 coordination of Cu(II) cation were occurred due to both enthalpic and entropic factors while the coordination of Cu(II) with their parent macrocyclic ligands 1 and 2 only enjoyed from only enthalpic advantages.

The advantage of spectrophotometric measurement for size-selective complexing of Cu(II) with O2N2-azacrown ligands.

A comparative investigation of the interaction of Cu(II) with a series of 15- to 19-membered mixed-donor dibenzo-substituted macrocyclic ligands, each incorporating an O2N2-donor set, has been carried out using UV-Visible studies in methanol. Although a ring size effect has been reported for a related series of Ni(II) complexes, no such metal ion discrimination has been reported for Cu(II) in terms of its binding constants with 14- to 17-membered macrocycles. Employing Job's method of continuous variation established 1:1 stoichiometry for the interaction between Cu(II) and 1-5. From UV-Visible studies applying the Benesi-Hildebrand equation, the binding constants (K) of Cu(II) with 1-5 were determined to be Cu(II)/1=3330 (±321) dm(3) mol(-1), Cu(II)/2=33,700 (±71) dm(3) mol(-1), Cu(II)/3=7260 (±151) dm(3) mol(-1), Cu(II)/4=57,000 (±257) dm(3) mol(-1) and Cu(II)/5=13,900 (±398) dm(3) mol(-1) in methanol at 25°C, respectively. The calculated binding constants showed a saw-tooth pattern in which 4 (18-membered ring) gives the highest K value for these complexes. The thermodynamic parameters (ΔG, ΔH, and TΔS) of the respective complexes have also been determined.