RESUMEN
Cadmium sulfide (CdS)-decorated, cross-linked melamine-formaldehyde polymer-based nanocomposite (MFP-CdS) has been synthesized. MFP-CdS is utilized here as a photoactive material for the photodegradation of six model organic dyes and their mixture in an aqueous medium in the presence of sunlight. The half-life values from the kinetic study of multiple dyes strongly support the importance of sunlight on the fast degradation of all six dyes compared to bulb light and control (dark) conditions. A comparative 1H NMR analysis of the dyes and their degraded products has been performed to support the breakdown of the aromatic framework of organic dyes using MFP-CdS in sunlight. The mechanisms involved in the photodegradation of dyes have been investigated based on radical trapping studies that support the significant involvement of superoxide radicals along with holes. Moreover, the dye removal efficiency using MFP-CdS from real industrial wastewater samples is evaluated via the external spiking of organic dyes and their mixture in unknown industrial effluents where they showed similar photodegradation results. Based on the high recyclability of MFP-CdS, these are used for multiple cycles.
RESUMEN
We have reported a one-pot two-step methodology for the synthesis of highly condensed heterocycles, pyrrolo[1,2-a][1,4]benzodiazepines, by a modified Pictet-Spengler reaction under mild conditions in a short time. Our approach has a few advantages over the conventional two components synthesis as it is step and atom economic, environmentally benign and a convergent synthetic method. We have discussed here the broad substrate scope of this novel methodology.
RESUMEN
This investigation highlights the role of counter anion towards the formation of thermo-responsive supramolecular assemblies of pre-defined discrete molecular Cu(ii) macrocycles. A new heteroditopic ligand (L) composed of two terminal triazolyl-pyridine units and a central pyridine-2,6-carboxamide unit connected via ethylene spacers predominantly forms dinuclear Cu(ii) macrocycles [L2Cu2]X4 (X = ClO4-, NO3-, Cl-) in the presence of respective monoanion-based Cu2+ salts. In contrast, dianionic SO42--based Cu2+ salt produces a mixture of both dinuclear [L2Cu2(SO4)2] and mononuclear [LCu(SO4)] Cu(ii) macrocycles. Importantly, detailed molecular structure determinations revealed the presence of multiple secondary interactions of the different counter anions with the corresponding macrocycles. The field emission scanning electron microscopy (FESEM) studies confirmed the ability of the individual macrocycles to further assemble upon slow evaporation of the solvent. Morphologically pure rod, sphere, and sheet-like superstructures were obtained for ClO4-, NO3-, and Cl- monoanion-based macrocycles, respectively. In contrast, a mixture of linear ribbon and microflower-like assemblies were obtained for SO42--based macrocycles. Moreover, it was found that upon heating, the rod-like assembly of [L2Cu2](ClO4)4 was gradually transformed into nanoparticles through a microparticle formation, which regenerated the rod-like assembly upon standing at room temperature. This was established from the FESEM, atomic force microscopy (AFM), and dynamic light scattering (DLS) studies.
RESUMEN
A hybrid tris-bidentate neutral ligand (L) composed of a central 2,2'-bipyridine and two terminal triazolyl-pyridine chelating units connected by methylene spacers is employed to synthesize trinuclear triple-stranded side-by-side helicates of first-row transition-metal(II) ions. Three such new homometallic helicates L3M3(OTf)6 [ M = Cu2+ (4); Ni2+ (5); Co2+ (6)], along with our recently reported helicates L3Fe3(OTf)6 (1), L3Zn3(OTf)6 (2), and L3Fe2Zn(OTf)6 (3) are taken into consideration for competitive formation and transmetalation studies. Single-crystal X-ray structures of L3Cu3(OTf)6 (4) and L3Ni3(OTf)6 (5) show the formation of trinuclear triple-stranded side-by-side helicates with alternating Λ and Δ chiralities at the metal ions as earlier observed in cases of L3Fe3(OTf)6 (1), L3Zn3(OTf)6 (2), and L3Fe2Zn(OTf)6 (3). ESI-FTICR mass spectrometry and UV-vis spectroscopy studies show that helicates L3Fe3(OTf)6 (1), L3Zn3(OTf)6 (2), L3Fe2Zn(OTf)6 (3), and L3Co3(OTf)6 (6) can easily be transmetalated to helicate L3Cu3(OTf)6 (4) in the presence of Cu(OTf)2. On the other hand, only a trace amount of heterometallic helicate L3Ni2Cu(OTf)6 forms even after several days, when Cu(OTf)2 is added to a the solution of homometallic helicate L3Ni3(OTf)6 (5). Further, we have demonstrated the formation of a heterometallic helicate L3Ni2Co(OTf)6 (7) from a 1:1:1 reaction mixture of L, Ni(OTf)2, and Co(OTf)2, which can also be prepared from homometallic helicate L3Co3(OTf)6 (6) by transmetalation with Ni(OTf)2.
RESUMEN
Formation of an ion-pair i.e. Fe2+ and [Cl2(H2O)2]2- coordination driven one dimensional (1D) smart supramolecular helical assembly of a new heteroditopic ligand was achieved. Moreover, thermo- and chemo-responsive transformation/disassembly/reassembly of the helical superstructure was also demonstrated.