Structural diversity in the series of lanthanide complexes [Ln(Ph3PO)n(NCS)3] (n = 3, 4)

Lawrence Chan; Simon A. Cotton; Joanna Dickson (nee Harris); Andrew W.G. Platt; Paul R. Raithby; Stefanie Schiffers; Alexander Tait; John E. Warren

doi:10.1016/j.poly.2022.115826

Structural diversity in the series of lanthanide complexes [Ln(Ph₃PO)_n(NCS)₃] (n = 3, 4)

Lawrence Chan, Simon A. Cotton, Joanna Dickson (nee Harris), Andrew W.G. Platt, Paul R. Raithby, Stefanie Schiffers, Alexander Tait, John E. Warren

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Abstract

Two unique series of lanthanide complexes [Ln(Ph₃PO)₄(NCS)₃] (Ln = La-Tb, except Pm) and [Ln(Ph₃PO)₃(NCS)₃] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph₃PO)₄(NCS)₃] crystallises in the monoclinic centrosymmetric space group P2₁/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph₃PO)₃(NCS)₃] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.

Original language	English
Article number	115826
Journal	Polyhedron
Volume	220
Early online date	12 Apr 2022
DOIs	https://doi.org/10.1016/j.poly.2022.115826
Publication status	Published - 1 Jul 2022

Bibliographical note

Funding Information:
We are grateful to the Engineering and Physical Sciences Research Council (UK) for a studentship to SS (EP/D072859/1) and for a Senior Fellowship to PRR (EP/D072859/1).

Funding

We are grateful to the Engineering and Physical Sciences Research Council (UK) for a studentship to SS (EP/D072859/1) and for a Senior Fellowship to PRR (EP/D072859/1).

Keywords

Crystal structures
Lanthanide contraction
Lanthanides
Phosphine oxide
Thiocyanate

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.poly.2022.115826

Polyhedron Author Accepted VersionAccepted author manuscript, 810 KBLicence: CC BY-NC-ND

Cite this

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title = "Structural diversity in the series of lanthanide complexes [Ln(Ph3PO)n(NCS)3] (n = 3, 4)",

abstract = "Two unique series of lanthanide complexes [Ln(Ph3PO)4(NCS)3] (Ln = La-Tb, except Pm) and [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph3PO)4(NCS)3] crystallises in the monoclinic centrosymmetric space group P21/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.",

keywords = "Crystal structures, Lanthanide contraction, Lanthanides, Phosphine oxide, Thiocyanate",

author = "Lawrence Chan and Cotton, {Simon A.} and {Dickson (nee Harris)}, Joanna and Platt, {Andrew W.G.} and Raithby, {Paul R.} and Stefanie Schiffers and Alexander Tait and Warren, {John E.}",

note = "Funding Information: We are grateful to the Engineering and Physical Sciences Research Council (UK) for a studentship to SS (EP/D072859/1) and for a Senior Fellowship to PRR (EP/D072859/1). ",

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T1 - Structural diversity in the series of lanthanide complexes [Ln(Ph3PO)n(NCS)3] (n = 3, 4)

AU - Chan, Lawrence

AU - Cotton, Simon A.

AU - Dickson (nee Harris), Joanna

AU - Platt, Andrew W.G.

AU - Raithby, Paul R.

AU - Schiffers, Stefanie

AU - Tait, Alexander

AU - Warren, John E.

N1 - Funding Information: We are grateful to the Engineering and Physical Sciences Research Council (UK) for a studentship to SS (EP/D072859/1) and for a Senior Fellowship to PRR (EP/D072859/1).

PY - 2022/7/1

Y1 - 2022/7/1

N2 - Two unique series of lanthanide complexes [Ln(Ph3PO)4(NCS)3] (Ln = La-Tb, except Pm) and [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph3PO)4(NCS)3] crystallises in the monoclinic centrosymmetric space group P21/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.

AB - Two unique series of lanthanide complexes [Ln(Ph3PO)4(NCS)3] (Ln = La-Tb, except Pm) and [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph3PO)4(NCS)3] crystallises in the monoclinic centrosymmetric space group P21/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.

KW - Crystal structures

KW - Lanthanide contraction

KW - Lanthanides

KW - Phosphine oxide

KW - Thiocyanate

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ER -

Structural diversity in the series of lanthanide complexes [Ln(Ph₃PO)_n(NCS)₃] (n = 3, 4)

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Senior Fellowship - TIME RESOLVED CRYSTALLOGRAPHY

Cite this

Structural diversity in the series of lanthanide complexes [Ln(Ph3PO)n(NCS)3] (n = 3, 4)

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

Senior Fellowship - TIME RESOLVED CRYSTALLOGRAPHY

Cite this

Structural diversity in the series of lanthanide complexes [Ln(Ph₃PO)_n(NCS)₃] (n = 3, 4)