E- or Z-Isomers Arising from the Geometries of Ligands in the Mercury Complex of 2-(Anthracen-9-ylmethylene)-N-phenylhydrazine Carbothioamide.

An anionic mercury(II) complex of 2-(anthracen-9-ylmethylene)-N-phenylhydrazine carbothioamide (HATU) and two isomers of a neutral mercury(II) complex of the anion of the same ligand (ATU) were reported. The anionic complex [Hg(HATU)2Cl2]·CH2Cl2 had a monodentate HATU ligand (a neutral form of the ligand) and chloride ligands. The two conformational isomers were of the neutral mercury(II) complex Hg(ATU)2·2DMF. The two isomers were from the E or Z geometry of the ligands across the conjugated C=N-N=C-N scaffold of the coordinated ligand. The two isomers of the complex were independently prepared and characterized. The spectroscopic properties of the isomers in solution were studied by 1H NMR as well as fluorescence spectroscopy. Facile conversion of the E-isomer to the Z-isomer in solution was observed. Density functional theory (DFT) calculations revealed that the Z-isomer of the complex was stable compared to the E-isomer by an energy of 14.35 kJ/mol; whereas, E isomer of the ligand was more stable than Z isomer by 8.37 KJ/mol. The activation barrier for the conversion of the E-isomer to the Z-isomer of the ligand was 167.37 kJ/mol. The role of the mercury ion in the conversion of the E-form to the Z-form was discussed. The mercury complex [Hg(HATU)2Cl2]·CH2Cl2 had the E-form of the ligand. Distinct photophysical features of these mercury complexes were presented.

Copper(II), Zinc(II), and Cadmium(II) Formylbenzoate Complexes: Reactivity and Emission Properties.

Synthesis, characterization, reactivity, and sensing properties of 4-formylbenzoate complexes of copper(II), zinc(II), and cadmium(II) possessing the 1,10-phenanthroline ancillary ligand are studied. The crystal structures of the (1,10-phenanthroline)bis(4-formylbenzoate)(aqua)copper(II) and (1,10-phenanthroline)bis(4-formylbenzo-ate)zinc(II) and a novel molecular complex comprising an assembly of mononuclear and dinuclear species of (1,10-phenanthroline)bis(4-formylbenzoate)cadmium(II) are reported. These zinc and cadmium complexes are fluorescent; they show differentiable sensitivity to detect three positional isomers of nitroaniline. The mechanism of sensing of nitroanilines by 1,10-phenanthroline and the complexes are studied by fluorescence titrations, photoluminescence decay, and dynamic light scattering. A plausible mechanism showing that 1,10-phenanthroline ligand-based emission quenched by electron transfer from the excited state of 1,10-phenanthroline to nitroaniline is supported by density functional theory calculations. In an anticipation to generate a fluorescent d10-copper(I) formylbenzoate complex by a mild reducing agent such as hydroxylamine hydrochloride for similar sensing of nitroaromatics as that of the d10-zinc and cadmium 4-formylbenzoate complexes, reactivity of d9-copper(II) with hydroxylamine hydrochloride in the presence of 4-formylbenzoic acid and 1,10-phenanthroline is studied. It did not provide the expected copper(I) complex but resulted in stoichiometry-dependent reactions of 4-formylbenzoic acid with hydroxylamine hydrochloride in the presence of copper(II) acetate and 1,10-phenanthroline. Depending on the stoichiometry of reactants, an inclusion complex of bis(1,10-phenanthroline)(chloro)copper(II) chloride with in situ-formed 4-((hydroxyimino)methyl)benzoic acid or copper(II) 4-(hydroxycarbamoyl)benzoate complex was formed. The self-assembly of the inclusion complex has the bis(1,10-phenanthroline)(chloro)copper(II) cation encapsulated in hydrogen-bonded chloride-hydrate assembly with 4-((hydroxyimino)methyl)benzoic acid.

Altered cropping pattern and cultural continuation with declined prosperity following abrupt and extreme arid event at ~4,200 yrs BP: Evidence from an Indus archaeological site Khirsara, Gujarat, western India.

Archaeological sites hold important clues to complex climate-human relationships of the past. Human settlements in the peripheral zone of Indus culture (Gujarat, western India) are of considerable importance in the assessment of past monsoon-human-subsistence-culture relationships and their survival thresholds against climatic stress exerted by abrupt changes. During the mature phase of Harappan culture between ~4,600-3,900yrsBP, the ~4,100±100yrsBP time slice is widely recognized as one of the major, abrupt arid-events imprinted innumerous well-dated palaeo records. However, the veracity of this dry event has not been established from any archaeological site representing the Indus (Harappan) culture, and issues concerning timing, changes in subsistence pattern, and the likely causes of eventual abandonment (collapse) continue to be debated. Here we show a significant change in crop-pattern (from barley-wheat based agriculture to 'drought-resistant' millet-based crops) at ~4,200 yrs BP, based on abundant macrobotanical remains and C isotopes of soil organic matter (δ13CSOM) in an archaeological site at Khirsara, in the Gujarat state of western India. The crop-change appears to be intentional and was likely used as an adaptation measure in response to deteriorated monsoonal conditions. The ceramic and architectural remains of the site indicate that habitation survived and continued after the ~4,200yrsBP dry climatic phase, but with declined economic prosperity. Switching to millet-based crops initially helped inhabitants to avoid immediate collapse due to climatic stresses, but continued aridity and altered cropping pattern led to a decline in prosperity levels of inhabitants and eventual abandonment of the site at the end of the mature Harappan phase.