Synthesis, Structure, and Bonding of Orthorhombic R5Au2Te2 (R = Lu, Ho, Dy, Y). Electronic Structure of the Binary Parent Valence Compound Eu5As4

Abstract

Four examples of R(5)Au(2)Te(2) (vec = 29 e(-); R = Lu, Ho, Dy, Y) have been synthesized by high-temperature solid-state techniques, isotypic examples of Tm(5)Sb(2)Si(2) (vec = 33 e(-)) and binary Eu(5)As(4) (vec = 30 e(-)). The crystal structure was established for Lu(5)Au(2)Te(2), (orthorhombic Cmce (No. 64), a = 15.056(2), b = 7.749(1), c = 7.754(1) Å, and Z = 4), in which pairs of tellurium layers alternate with two-dimensional (2D) Lu(5)Au(2) slabs that are aggregated in such a way that each Au(2)-centered bi-trigonal prism (BTP) of Lu interconnects four other identical units, with the remaining cavities filled by nominal body-centered Lu cubes. The metal-metal aggregation in this structure provides a novel building unit in ternary rare-earth-metal-rich tellurides. Linear-muffin-tin-orbital (LMTO) electronic structure calculations and COHP analyses reveal that Lu(5)Au(2)Te(2) is a poor metal with Au(2) dimers and strong polar Lu-Au and Lu-Te interactions. The first theoretical analysis of the binary parent structure Eu(5)As(4) (vec = 30 e(-)) provides a simpler description of the equivalent orbital interactions and a closed shell gap in terms of the idealized (Eu(2+))(5)(As(2)(4-))(As(3-))(2) representation, particularly for the explicit filled As(2) levels σ(s), σ(s)*, σ(p), π, π*, plus empty σ(p)*. Crystal Orbital Hamilton Population (-COHP) data illuminate the prominent roles that polar bonding of Eu-As or Lu-Te and Lu-Au and relativistic effects with gold play in these, the former corresponding to 83% and 86% of the total Hamilton population for Eu(5)As(4) and Lu(5)Au(2)Te(2), respectively.