Antiperovskite Nitridophosphate Oxide Ho3[PN4]O by High‐Pressure Metathesis. Issue 13 (4th April 2017)

• Record Type: Journal Article
• Authors: Kloß, Simon D.; Weidmann, Niels; Schnick, Wolfgang
• Is Part Of: European journal of inorganic chemistry. Issue 13(2017)
• Page Start: 1930
• Page End: 1937
• Publication Date: 2017-04-04
• Subjects: High‐pressure chemistry -- Nitrides -- Metathesis -- Rare earths -- Solid‐state structures; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201601425
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Rare‐earth nitridophosphates are a recently discovered class of materials, which are accessible by high‐pressure metathesis. Antiperovskite‐type Ho3 [PN4 ]O was synthesized from HoF3, LiPN2, Li3 N, and Li2 O at 5 GPa and ca. 1025 °C by this method and the multianvil technique. Ho3 [PN4 ]O contains rarely observed isolated PN4 tetrahedra and can be derived by the hierarchical substitution of the ABX3 perovskite, in which Ho occupies the X positions, O occupies the B position, and the PN4 tetrahedra occupy the A position. The structure was refined on the basis of powder diffraction data [ I 4/ mcm, a = 6.36112(3), c = 10.5571(1) Å, Z = 4, R wp = 0.04, R Bragg = 0.01, χ 2 = 2.275] starting from the structural model of isotypic Gd3 [SiN3 O]O. To characterize Ho3 [PN4 ]O, elemental analyses were performed through energy‐dispersive X‐ray spectroscopy (EDX) and inductively coupled plasma optical emission spectroscopy (ICP‐OES). Ho3 [PN4 ]O is paramagnetic down to low temperatures with µ eff = 10.43(1) µB and a Curie temperature ( Θ ) of 0.11(4) K. It shows the optical characteristics of Ho 3+ ions and vibrations corresponding to isolated PN4 tetrahedra. On the basis of DFT calculations [generalized gradient approximation (GGA)], Ho3 [PN4 ]O has an indirect band gap of 1.87 eV. We demonstrate the versatility of high‐pressure metathesis by attaining the low end of the P/N atomic ratio κ = 1/4. This confirms the previous assumption that rare‐earth nitridophosphates with κ = 1/2 to 1/4 are feasible by this method. Abstract : Ho3 [PN4 ]O, a rare‐earth nitridophosphate oxide with isolated PN4 tetrahedra, is prepared by high‐pressure metathesis. Ho3 [PN4 ]O adopts an antiperovskite structure with PN4 tetrahedra in the cuboctahedral voids. This synthesis is a stepping stone for the high‐pressure metathesis of nitridophosphates.