Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide
Lanthanoid picrate (pic) complexes of 5,11,17,23-tetra-tert-butyl-25-hydroxy-26,27,28-tris(diethylcarbamoylmethoxy)calix[4]arene (LH) have been synthesised and structurally characterised, to complete this series for all lanthanoids (other than promethium). From cerium to lutetium, three structural t...
| Main Authors: | , , , , , |
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| Format: | Journal Article |
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CSIRO Publishing
2017
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| Online Access: | http://hdl.handle.net/20.500.11937/69510 |
| _version_ | 1848762060648742912 |
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| author | Nealon, G. McIldowie, M. Skelton, B. Mocerino, Mauro Massi, Massimiliano Ogden, Mark |
| author_facet | Nealon, G. McIldowie, M. Skelton, B. Mocerino, Mauro Massi, Massimiliano Ogden, Mark |
| author_sort | Nealon, G. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | Lanthanoid picrate (pic) complexes of 5,11,17,23-tetra-tert-butyl-25-hydroxy-26,27,28-tris(diethylcarbamoylmethoxy)calix[4]arene (LH) have been synthesised and structurally characterised, to complete this series for all lanthanoids (other than promethium). From cerium to lutetium, three structural types are observed: Type I, [Ln(L)(O,O'-pic)](pic), Ln = Ce-Dy; Type II, [Ln(L)(O-pic)](pic), Ln = Tb, Ho; Type III, [Ln(L)(HOEt)](pic)2, Ln = Er-Lu. With lanthanum, three different ten-coordinate complexes were characterised; [Ln(L)(O,O'-pic)(HOEt)](pic), [Ln(L)(O,O'-pic)(OH2)](pic), and [Ln(L)(O,O'-pic)(HOMe)](pic). The crystallisation of Type I and II observed for terbium shows that the stability of the different structures are sensitively poised at the transition points. Nevertheless, the structures show that the vacant space in the coordination sphere left by the trisamide L tends to reduce across the series as expected. It is occupied by a bidentate picrate anion and unidentate solvent molecule with lanthanum, a bidentate picrate anion for cerium to dysprosium (Type I), a unidentate picrate anion for terbium and holmium (Type II), and finally a unidentate solvent molecule from erbium to lutetium (Type III). The coordination number thus reduces from 10 to 8 across the series. |
| first_indexed | 2025-11-14T10:41:34Z |
| format | Journal Article |
| id | curtin-20.500.11937-69510 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T10:41:34Z |
| publishDate | 2017 |
| publisher | CSIRO Publishing |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-695102018-08-28T00:24:17Z Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide Nealon, G. McIldowie, M. Skelton, B. Mocerino, Mauro Massi, Massimiliano Ogden, Mark Lanthanoid picrate (pic) complexes of 5,11,17,23-tetra-tert-butyl-25-hydroxy-26,27,28-tris(diethylcarbamoylmethoxy)calix[4]arene (LH) have been synthesised and structurally characterised, to complete this series for all lanthanoids (other than promethium). From cerium to lutetium, three structural types are observed: Type I, [Ln(L)(O,O'-pic)](pic), Ln = Ce-Dy; Type II, [Ln(L)(O-pic)](pic), Ln = Tb, Ho; Type III, [Ln(L)(HOEt)](pic)2, Ln = Er-Lu. With lanthanum, three different ten-coordinate complexes were characterised; [Ln(L)(O,O'-pic)(HOEt)](pic), [Ln(L)(O,O'-pic)(OH2)](pic), and [Ln(L)(O,O'-pic)(HOMe)](pic). The crystallisation of Type I and II observed for terbium shows that the stability of the different structures are sensitively poised at the transition points. Nevertheless, the structures show that the vacant space in the coordination sphere left by the trisamide L tends to reduce across the series as expected. It is occupied by a bidentate picrate anion and unidentate solvent molecule with lanthanum, a bidentate picrate anion for cerium to dysprosium (Type I), a unidentate picrate anion for terbium and holmium (Type II), and finally a unidentate solvent molecule from erbium to lutetium (Type III). The coordination number thus reduces from 10 to 8 across the series. 2017 Journal Article http://hdl.handle.net/20.500.11937/69510 10.1071/CH17484 CSIRO Publishing fulltext |
| spellingShingle | Nealon, G. McIldowie, M. Skelton, B. Mocerino, Mauro Massi, Massimiliano Ogden, Mark Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide |
| title | Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide |
| title_full | Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide |
| title_fullStr | Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide |
| title_full_unstemmed | Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide |
| title_short | Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide |
| title_sort | structural variations in the complete series of lanthanoid complexes of a calix[4]arene trisamide |
| url | http://hdl.handle.net/20.500.11937/69510 |