29Si, 47Ti, 49Ti and 195Pt solid state MAS NMR spectroscopic investigations of ternary silicides TPtSi, germanides TPtGe (T = Ti, Zr, Hf) and stannide TiPtSn

Abstract

Eight ternary tetrelides TPtX (T = Ti, Zr, Hf; X = Si, Ge, Sn) were synthesized from the elements by arc-melting and subsequent annealing. TiPtSi, ZrPtSi, ZrPtGe, HfPtSi and HfPtGe crystallize with the orthorhombic TiNiSi type structure, in the space group Pnma. The structures of HfPtSi (a = 654.44(9), b = 387.97(6), c = 750.0(1) pm, wR₂ = 0.0592, 411 F² values, 20 variables) and HfPtGe (a = 660.36(7), b = 395.18(4), c = 763.05(8) pm, wR₂ = 0.0495, 430 F² values, 20 variables) were refined from single crystal X-ray diffractometer data. TiPtSn adopts the cubic MgAgAs type. TiPtGe is dimorphic with a TiNiSi type high-temperature modification which transforms to cubic LT-TiPtGe (MgAgAs type). All phases were investigated by high resolution ²⁹Si, ⁴⁷Ti, ⁴⁹Ti and ¹⁹⁵Pt solid state MAS NMR spectroscopy. In the cubic compounds, the ^47/49Ti NMR signals are easily detected owing to the absence of quadrupolar broadening effects. The ¹⁹⁵Pt resonances of the orthorhombic compounds are characterized by strongly negative isotropic Knight shifts and large Knight shift anisotropies, whereas positive isotropic Knight shifts and no anisotropies are observed for the cubic compounds. These results indicate that the phase transition in TiPtGe is associated with dramatic changes in the electronic properties. Within each group of isotypic compounds the isotropic ²⁹Si, ^47/49Ti and ¹⁹⁵Pt Knight shifts show systematic dependences on the transition metal or tetrel atomic number, suggesting that the numerical values are influenced by the electronegativities of the metallic (or metalloid) neighbours.