Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands
A family of four tris-carboxylic acid ligands 1,3,5-tris(4′-carboxybiphenyl-2-yl)benzene (H3L1), 1,3,5-tris-2-carboxyphenylbenzene (H3L2), 1,3,5-tris(4″-carboxy-para-terphenyl-2-yl)benzene (H3L3) and 1,3,5-tris(3′-carboxybiphenyl-2-yl)benzene (H3L4) have been synthesised and reacted with first row t...
| Main Authors: | , , , , , , , , , , , |
|---|---|
| Format: | Article |
| Published: |
Elsevier
2016
|
| Subjects: | |
| Online Access: | https://eprints.nottingham.ac.uk/46674/ |
| _version_ | 1848797378641920000 |
|---|---|
| author | Argent, Stephen P. Tarassova, Irina Greenaway, Alex Nowell, Harriot Barnett, Sarah A. Warren, Mark R. Tang, Chiu C. Morris, Christopher G. Lewis, William Champness, Neil R. Schröder, Martin Blake, Alexander J. |
| author_facet | Argent, Stephen P. Tarassova, Irina Greenaway, Alex Nowell, Harriot Barnett, Sarah A. Warren, Mark R. Tang, Chiu C. Morris, Christopher G. Lewis, William Champness, Neil R. Schröder, Martin Blake, Alexander J. |
| author_sort | Argent, Stephen P. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | A family of four tris-carboxylic acid ligands 1,3,5-tris(4′-carboxybiphenyl-2-yl)benzene (H3L1), 1,3,5-tris-2-carboxyphenylbenzene (H3L2), 1,3,5-tris(4″-carboxy-para-terphenyl-2-yl)benzene (H3L3) and 1,3,5-tris(3′-carboxybiphenyl-2-yl)benzene (H3L4) have been synthesised and reacted with first row transition metal cations to give nine complexes which have been structurally characterised by X-ray crystallography. The ligands share a common design motif having three arms connected to a benzene core via three ortho-disubstituted phenyl linkers. The ligands vary in length and direction of the carboxylic acid functionalised arms and are all able to adopt tripodal conformations in which the three arms are directed facially. The structures of [Zn8(μ4-O)(L1)4(HCO2)2(H2O)0.33(DMF)2] (1a-Zn), [Co14(L2)6((μ3-OH)8(HCO2)2(DMF)4(H2O)6] (2-Co), [Ni14(L2)6(μ3-OH)8(HCO2)2(DMF)4(H2O)6] (2-Ni), [Zn8(μ4-O)(L3)4(DMF)(H2O)4(NO3)2] (3-Zn), [Ni5(μ-OH)4(L2)2(H2O)6(DMF)4] (5-Ni), [Co8(μ4-O)4(L4)4(DMF)3(H2O)] (6-Co) and Fe3(μ3-O)(L4)2(H2O)(DMF)2)] (7-Fe) contain polynuclear clusters surrounded by ligands (L1–4)3− in tripodal conformations. The structure of [Zn2(HL1)2(DMF)4] (1b-Zn) shows it to be a binuclear complex in which the two ligands (HL2)2− are partially deprotonated whilst {[Zn3(L2)2(DMF)(H2O)(C5H5N)]·6(DMF)}n (4-Zn) is a 2D coordination network containing {Zn2(RCO2)4(solv)2} paddlewheel units. The conformations of the ligand arms in the complexes have been analysed, confirming that the shared ortho-disubstituted phenyl ring motif is a powerful and versatile tool for designing ligands able to form high-nuclearity coordination clusters when reacted with transition metal cations. |
| first_indexed | 2025-11-14T20:02:56Z |
| format | Article |
| id | nottingham-46674 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:02:56Z |
| publishDate | 2016 |
| publisher | Elsevier |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-466742020-05-04T18:25:55Z https://eprints.nottingham.ac.uk/46674/ Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands Argent, Stephen P. Tarassova, Irina Greenaway, Alex Nowell, Harriot Barnett, Sarah A. Warren, Mark R. Tang, Chiu C. Morris, Christopher G. Lewis, William Champness, Neil R. Schröder, Martin Blake, Alexander J. A family of four tris-carboxylic acid ligands 1,3,5-tris(4′-carboxybiphenyl-2-yl)benzene (H3L1), 1,3,5-tris-2-carboxyphenylbenzene (H3L2), 1,3,5-tris(4″-carboxy-para-terphenyl-2-yl)benzene (H3L3) and 1,3,5-tris(3′-carboxybiphenyl-2-yl)benzene (H3L4) have been synthesised and reacted with first row transition metal cations to give nine complexes which have been structurally characterised by X-ray crystallography. The ligands share a common design motif having three arms connected to a benzene core via three ortho-disubstituted phenyl linkers. The ligands vary in length and direction of the carboxylic acid functionalised arms and are all able to adopt tripodal conformations in which the three arms are directed facially. The structures of [Zn8(μ4-O)(L1)4(HCO2)2(H2O)0.33(DMF)2] (1a-Zn), [Co14(L2)6((μ3-OH)8(HCO2)2(DMF)4(H2O)6] (2-Co), [Ni14(L2)6(μ3-OH)8(HCO2)2(DMF)4(H2O)6] (2-Ni), [Zn8(μ4-O)(L3)4(DMF)(H2O)4(NO3)2] (3-Zn), [Ni5(μ-OH)4(L2)2(H2O)6(DMF)4] (5-Ni), [Co8(μ4-O)4(L4)4(DMF)3(H2O)] (6-Co) and Fe3(μ3-O)(L4)2(H2O)(DMF)2)] (7-Fe) contain polynuclear clusters surrounded by ligands (L1–4)3− in tripodal conformations. The structure of [Zn2(HL1)2(DMF)4] (1b-Zn) shows it to be a binuclear complex in which the two ligands (HL2)2− are partially deprotonated whilst {[Zn3(L2)2(DMF)(H2O)(C5H5N)]·6(DMF)}n (4-Zn) is a 2D coordination network containing {Zn2(RCO2)4(solv)2} paddlewheel units. The conformations of the ligand arms in the complexes have been analysed, confirming that the shared ortho-disubstituted phenyl ring motif is a powerful and versatile tool for designing ligands able to form high-nuclearity coordination clusters when reacted with transition metal cations. Elsevier 2016-12-14 Article PeerReviewed Argent, Stephen P., Tarassova, Irina, Greenaway, Alex, Nowell, Harriot, Barnett, Sarah A., Warren, Mark R., Tang, Chiu C., Morris, Christopher G., Lewis, William, Champness, Neil R., Schröder, Martin and Blake, Alexander J. (2016) Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands. Polyhedron, 120 . pp. 18-29. ISSN 1873-3719 High nuclearity cluster; Metal-directed assembly; Carboxylate bridging; Basic carboxylate; Crystal structure http://www.sciencedirect.com/science/article/pii/S0277538716301127 doi:10.1016/j.poly.2016.04.029 doi:10.1016/j.poly.2016.04.029 |
| spellingShingle | High nuclearity cluster; Metal-directed assembly; Carboxylate bridging; Basic carboxylate; Crystal structure Argent, Stephen P. Tarassova, Irina Greenaway, Alex Nowell, Harriot Barnett, Sarah A. Warren, Mark R. Tang, Chiu C. Morris, Christopher G. Lewis, William Champness, Neil R. Schröder, Martin Blake, Alexander J. Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands |
| title | Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands |
| title_full | Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands |
| title_fullStr | Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands |
| title_full_unstemmed | Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands |
| title_short | Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands |
| title_sort | assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands |
| topic | High nuclearity cluster; Metal-directed assembly; Carboxylate bridging; Basic carboxylate; Crystal structure |
| url | https://eprints.nottingham.ac.uk/46674/ https://eprints.nottingham.ac.uk/46674/ https://eprints.nottingham.ac.uk/46674/ |