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.