The interplay of secondary Hg⋯S, Hg⋯N and Hg⋯π bonding interactions in supramolecular structures of phenylmercury(ii) dithiocarbamates

Three new phenylmercury(II) and one mercury(II) dithiocarbamate complexes viz. PhHg S2CN(PyCH2) Bz (1), PhHg S2CN(PyCH2)CH3 (2), PhHg S2CN(Bz)CH3 (3), and [Hg (NCS2(PyCH2)Bz)(2)] (4) (Py = pyridine; Bz = benzyl) have been synthesized and characterized by elemental analyses, IR, electronic absorption, H-1 and C-13 NMR spectroscopy. The crystal structures of 1, 2 and 3 showed a linear S-Hg-C core at the centre of the molecule, in which the metal atom is bound to the sulfur atom of the dithiocarbamate ligand and a carbon atom of the aromatic ring. In contrast the crystal structure of 4 showed a linear S-Hg-S core at the Hg(II) centre of the molecule. Weak intermolecular Hg center dot center dot center dot N (Py) interactions link molecules into a linear chain in the case of 1, whereas chains of dimers are formed in 2 through intermolecular Hg center dot center dot center dot N (Py) and Hg center dot center dot center dot S interactions. 3 forms a conventional face-to-edge dimeric structure through intermolecular Hg center dot center dot center dot S secondary bonding and 4 forms a linear chain of dimers through face-to-face Hg center dot center dot center dot S secondary bonding. In order to elucidate the nature of these secondary bonding interactions and the electronic absorption spectra of the complexes, ab initio quantum chemical calculations at the MP2 level and density functional theory calculations were carried out for 1-3. Complexes 1 and 2 exhibited photoluminescent properties in the solid state as well as in the solution phase. Studies indicate that Hg center dot center dot center dot S interactions decrease and Hg center dot center dot center dot N interactions increase the chances of photoluminescence in the solid phase

Peaceful coexistence? The role of religious schools and NGOs in the growth of female secondary schooling in Bangladesh

Bangladesh Rural Advancement Committee (BRAC), a non-governmental organisation (NGO), runs a large number of non-formal primary schools in Bangladesh which target out-of-school children from poor families. These schools are well-known for their effectiveness in closing the gender gap in primary school enrolment. On the other hand, registered non-government secondary madrasas (or Islamic schools) today enrol one girl against every boy student. In this article, we document a positive spillover effect of BRAC schools on female secondary enrolment in registered madrasas. Drawing upon school enrolment data aggregated at the region level, we first show that regions that had more registered madrasas experienced greater secondary female enrolment growth during 1999–2003, holding the number of secular secondary schools constant. In this context we test the impact of BRAC-run primary schools on female enrolment in registered madrasas. We deal with the potential endogeneity of placement of BRAC schools using an instrumental variable approach. Controlling for factors such as local-level poverty, road access and distance from major cities, we show that regions with a greater presence of BRAC schools have higher female enrolment growth in secondary madrasas. The effect is much bigger when compared to that on secondary schools.