In:
Chemistry – A European Journal, Wiley, Vol. 28, No. 9 ( 2022-02-16)
Abstract:
Centrosymmetric skutterudite RhP 3 was converted to a nonsymmorphic and chiral compound RhSi 0.3 P 2.7 (space group P 2 1 2 1 2 1 ) by means of partial replacement of Si for P. The structure, determined by a combination of X‐ray crystallography and solid state 31 P NMR, exhibits branched polyanionic P/Si chains that are unique among metal phosphides. A driving force to stabilize the locally noncentrosymmetric cis‐ RhSi 2 P 4 and fac‐ RhSi 3 P 3 fragments is π‐electron back‐donation between the Rh t 2g ‐type orbitals and the unoccupied antibonding Si/P orbitals, which is more effective for Si than for P. In situ studies and total energy calculations revealed the metastable nature of RhSi 0.3 P 2.7 . Electronic structure calculations predicted centrosymmetric cubic RhP 3 to be metallic which was confirmed by transport properties measurements. In contrast, the electronic structure for chiral orthorhombic RhSi 0.3 P 2.7 contained a bandgap, and this compound was shown to be a narrow gap semiconductor.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.202104319
Language:
English
Publisher:
Wiley
Publication Date:
2022
detail.hit.zdb_id:
1478547-X
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