Unusually short unsupported Au(III)⋯Au(III) aurophilic contacts in emissive lanthanide tetracyanoaurate(III) complexes.

A series of [Au(CN)4]- salts with lanthanide 2,2'-bipyridine dioxide cations features Au(III) aurophilic interactions between [Au(CN)4]- groups, with Au⋯Au distances of 3.3603(4) Šand 3.4354(4) Šthat are shorter than any previously reported. Computations predict the interactions to be weakly attractive; packing effects appear to also contribute to the close contacts. The materials are emissive: there is no Au(III)-based luminescence, but for Ln = Eu the PLQY of 29% is surprisingly high compared to related analogues.

Anisotropic Thermal Expansion of Structurally Related Lanthanide-Mercury(II) Cyanide Coordination Polymers.

Three sets of related lanthanide-mercury(II) cyanide coordination polymers were synthesized by the reaction of LnCl3·xH2O (Ln = Ce, Nd, Eu, Gd, Tb, Dy, Ho, Tm, Yb, and Lu) with Hg(CN)2 and structurally characterized. [Ce(OH2)5][Hg(CN)2Cl]3·2H2O is a 3-D material with sheet-based architecture; its thermal expansion behavior shows uniaxial negative thermal expansion (-18.3(8), 39(2), and 68.3(16) ppm K-1 along the a, b, and c axes, respectively). This anisotropic thermal behavior is postulated to be driven elastically by weak Hg···Cl interactions: large area expansion of the sheets causes negative thermal expansion in the perpendicular direction. Using lanthanides heavier than Ce yielded 2-D sheet-based compounds with the formula [Ln(OH2)x]2[Hg(CN)2]5Cl6·2H2O (Ln = Nd and Eu, x = 7; Ln = Gd, Tb, Dy, Ho, Tm, Yb, and Lu, x = 6). Although there was also evidence for elastic behavior within these materials, both showed uniaxial zero thermal expansion (Ln = Nd: 27.9(17), 22.4(10), and 0.6(12) ppm K-1 along the I, II, and III principal axes, respectively; Ln = Tb: 39.6(12), 1.1(17), and 36.1(7) ppm K-1 along the a, b, and c axes, respectively). Despite their similar structural architecture, this zero thermal expansion was found to occur in different directions─within the plane of the 2-D sheets for [Nd(OH2)7]2[Hg(CN)2]5Cl6·2H2O but in the direction perpendicular to the 2-D sheets for [Tb(OH2)6]2[Hg(CN)2]5Cl6·2H2O. Overall, this system of compounds reveals the delicate relationship between coordination polymer structure and thermal expansion.