PdGeS3—A Novel One-Dimensional Metathiogermanate

Abstract

The novel compound PdGeS 3 has been synthesized by direct reaction of the elements at 600 8C. Single crystals of the fibrous material were grown in a molten flux of NaSCN. The crystal structure was determined by single-crystal X-ray diffraction techniques. PdGeS 3 crystallizes in the monoclinic space group C2/m (a 14.217(6), 2À einer single chains. The palladium atoms connecting these chains reside in distorted squareplanar environments surrounded by four sulfur atoms. High anisotropy of chemical bonding emerged because interactions between the strands consisist of van der Waals forces exclusively. The juxtaposition of the double chains is similar to a two-dimensional hexagonal close-packed arrangement. The electronic structure and bonding is analyzed in real space by means of the electron localization function (ELF) resulting from self-consistent LMTO band structure calculations. Peculiarities in the atomic arrangement of the strands are explained by the spatial requirements of the lone pairs of electrons on sulfur and their interactions with the palladium atoms. The mutual dependencies of the bonding within and between the chains are discussed by using a two-dimensional ELF map.

High electron mobility and wide-bandgap properties in a novel 1D PdGeS3 nanochain

“…The bulk compound PdGeS 3 , synthesized by the direct reaction of the elements at 600 °C, is a typical quasi-1D vdW material. 41 As depicted in Fig. 1(a), the optimized structure of bulk PdGeS 3 is composed of two 1D nanochains arranged along the x axis parallelly bonded by vdW interactions to form a monoclinic crystal which belongs to the space group C 2/ m (No.…”

“…The fully relaxed lattice constants of bulk PdGeS 3 are a = −3.49 Å, b = 14.28 Å, c = 9.11 Å, and α = 107.54°, which are in good agreement with previous experimental results ( a = 3.45 Å, b = 14.22 Å, c = 9.08 Å, and α = 106.58°). 41 As shown in Fig. 1(b), in each PdGeS 3 nanochain, two opposite strands of corner-sharing GeS 4 tetrahedra are connected by Pd atoms, forming rectangular PdS 4 pyramids, which are similar to the 2D hexagonal close-packed arrangement.…”

“…The bulk compound PdGeS 3 , first synthesized in 1980, is a typical quasi-1D nanochain material and the alternating nanochains are linked by vdW interactions. 41 Such a vdW chain structure shows that PdGeS 3 is a potential candidate for 1D materials. However, the corresponding structures and properties of this 1D PdGeS 3 nanochain are still unexplored.…”

Spectrum of Exfoliable 1D van der Waals Molecular Wires and Their Electronic Properties

“…We choose representative materials from the families and simple wire prototypes to evaluate using density functional theory calculations. Materials from the common structural families SbSeI, TaTlSe 3 , and HfI 3 were selected in addition to PdBr 2 , PNF 2 , , and GePdS 3 , which display simple, spatially separated wire compositions. We also perform calculations on materials that exhibit wire-like character but insufficient spacing between wires to satisfy the screening criteria of Cheon et al .…”

Thioaluminogermanate M(AlS2)(GeS2)4 (M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion-Exchange and Solid-State 27Al and 23Na NMR Spectroscopy

“…The A /Al/Ge/S ( A = alkali metal, transition metal) family remains largely unexplored, and only two structures are reported to date, Rb 3 (Al Q 2 ) 3 (Ge Q 2 ) 7 ( Q = S, Se) and A (AlS 2 )­(GeS 2 ) ( A = Na, K) . The thiogermanates were mainly synthesized by conventional solid-state and hydro­(solvo)­thermal synthetic routes. − One of the most powerful methods is the reactive molten alkali-metal polysulfide flux, which has been employed in the exploratory synthesis of a large set of ternary and quaternary thiogermanates. , The advantage of using alkali metals is primarily due to their reactivity with sulfur at low temperatures and their influence on the dimensionality and the crystallinity of the subject compounds …”