Semiconducting Lead−Sulfur−Organic Network Solids

Abstract

The reactions of Pb(OAc)2 with 1,2,4,5-benzenetetrathiol, 1,4-benzenedithiol, and benzenehexathiol in ethylenediamine yield bright yellow [Pb2(S2C6H2S2)(en)]n, orange-red [Pb3(SC6H4S)3(en)2]n, and brown [Pb3C6S6]n, respectively. The structures of [Pb2(S2C6H2S2)(en)]n and [Pb3C6S6]n were solved by synchrotron X-ray powder diffraction, while the structure of [Pb3(SC6H4S)3(en)2]n was solved by single-crystal X-ray diffraction. The bonding in [Pb2(S2C6H2S2)(en)]n indicates the presence of "molecular" units, while in [Pb3C6S6]n, the bonding most resembles that in an inorganic solid such as PbS. The differences in bonding are reflected in the optical and electrical properties of the materials; [Pb3C6S6]n is a semiconductor.

Electrically Conductive Porous Metal–Organic Frameworks

“…Fore xample, because the electronegativity values for transition metals are better matched with that of sulfur than that of oxygen (redox matching), [40] metal-organic chains or sheets connected through metal-sulfur bonds are expected to provide better charge transport pathways than structurally analogous metal-oxygen chains/sheets.S emiconducting coordination polymers based on metal-sulfur chains have been reported, [41,42] and this idea is also applicable to MOFs. This concept of redox matching has been illustrated in the M 2 (DOBDC) frameworks (M = Mg, Mn, Fe,Co, Ni, Cu, Zn, DOBDC 4À = 2,5-dihydroxybenzene-1,4-dicarboxylate).…”

Five novel dicyanidoaurate(i)-based complexes exhibiting significant biological activities: synthesis, characterization and three crystal structures

“…For the crystal structure determination, the single-crystals of [Cu(hydeten) 2 . Data collection: X-Area, cell refinement: X-Area, data reduction: XRED.…”

Effects of reduced dimensionality on the electronic structure and defect chemistry of semiconducting hybrid organic–inorganic PbS solids

“…Crystal structures for one-dimensional and three-dimensional hybrid organicinorganic PbS composite networks have recently been determined (Turner et al 2008), which are illustrated in figure 1. The experimental structural parameters, measured at room temperature using powder X-ray diffraction, were taken as the starting positions, which were then fully relaxed through DFT calculations, with the resulting equilibrium structures and band gaps detailed in table 1.…”

“…For example, Pb 3 (C 6 S 6 ) contains three-dimensional networks of edge-sharing PbS cubes, while Pb 2 (S 4 C 6 H 2 )(en), where en represents the ethylenediamine ligand, contains one-dimensional kinked chains of PbS stacked along the triclinic a-axis. These two materials exhibit optical band gaps of 1.7 and 3.1 eV, respectively (Turner et al 2008), covering the full range of the visible spectrum. This demonstrates the potential of hybrid materials for optoelectronic applications including photovoltaics and solid-state lighting, areas traditionally dominated by III-V, II-VI and related semiconductor alloys (Srivastava et al 1985;Wei et al 1990;Zhu et al 2008;Chen et al 2009b;Catlow et al 2010).…”