Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands

Stephen P. Argent; Irina Tarassova; Alex Greenaway; Harriot Nowell; Sarah A. Barnett; Mark R. Warren; Chiu C. Tang; Christopher Morris; William Lewis; Neil R. Champness; Martin Schröder; Alexander J. Blake

doi:10.1016/j.poly.2016.04.029

Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands

Stephen P. Argent, Irina Tarassova, Alex Greenaway, Harriot Nowell, Sarah A. Barnett, Mark R. Warren, Chiu C. Tang, Christopher Morris, William Lewis, Neil R. Champness^*, Martin Schröder, Alexander J. Blake

^*Corresponding author for this work

The University of Manchester

Research output: Contribution to journal › Article › peer-review

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Abstract

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)(L ⁴)₂(H₂O)(DMF)₂)] (7-Fe) contain polynuclear clusters surrounded by ligands (L^1-4 )^3- in tripodal conformations. The structure of [Zn₂(HL ¹ )₂(DMF)₄] (1b-Zn) shows it to be a binuclear complex in which the two ligands (HL² )^2- are partially deprotonated whilst ([Zn₃(L ² )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.

Original language	English
Journal	Polyhedron
Early online date	30 Apr 2016
DOIs	https://doi.org/10.1016/j.poly.2016.04.029
Publication status	Published - 2016

Keywords

Basic carboxylate
Carboxylate bridging
Crystal structure
High nuclearity cluster
Metal-directed assembly

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10.1016/j.poly.2016.04.029

schroder_manuscript (2)Accepted author manuscript, 6.92 MB

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@article{553f3100b912465a89ad2dcdb7a6267d,

title = "Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands",

abstract = "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)(L 4 )2(H2O)(DMF)2)] (7-Fe) contain polynuclear clusters surrounded by ligands (L1-4 )3- in tripodal conformations. The structure of [Zn2(HL 1 )2(DMF)4] (1b-Zn) shows it to be a binuclear complex in which the two ligands (HL2 )2- are partially deprotonated whilst ([Zn3(L 2 )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.",

keywords = "Basic carboxylate, Carboxylate bridging, Crystal structure, High nuclearity cluster, Metal-directed assembly",

author = "Argent, \{Stephen P.\} and Irina Tarassova and Alex Greenaway and Harriot Nowell and Barnett, \{Sarah A.\} and Warren, \{Mark R.\} and Tang, \{Chiu C.\} and Christopher Morris and William Lewis and Champness, \{Neil R.\} and Martin Schr{\"o}der and Blake, \{Alexander J.\}",

year = "2016",

doi = "10.1016/j.poly.2016.04.029",

language = "English",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands

AU - Argent, Stephen P.

AU - Tarassova, Irina

AU - Greenaway, Alex

AU - Nowell, Harriot

AU - Barnett, Sarah A.

AU - Warren, Mark R.

AU - Tang, Chiu C.

AU - Morris, Christopher

AU - Lewis, William

AU - Champness, Neil R.

AU - Schröder, Martin

AU - Blake, Alexander J.

PY - 2016

Y1 - 2016

N2 - 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)(L 4 )2(H2O)(DMF)2)] (7-Fe) contain polynuclear clusters surrounded by ligands (L1-4 )3- in tripodal conformations. The structure of [Zn2(HL 1 )2(DMF)4] (1b-Zn) shows it to be a binuclear complex in which the two ligands (HL2 )2- are partially deprotonated whilst ([Zn3(L 2 )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.

AB - 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)(L 4 )2(H2O)(DMF)2)] (7-Fe) contain polynuclear clusters surrounded by ligands (L1-4 )3- in tripodal conformations. The structure of [Zn2(HL 1 )2(DMF)4] (1b-Zn) shows it to be a binuclear complex in which the two ligands (HL2 )2- are partially deprotonated whilst ([Zn3(L 2 )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.

KW - Basic carboxylate

KW - Carboxylate bridging

KW - Crystal structure

KW - High nuclearity cluster

KW - Metal-directed assembly

UR - https://www.scopus.com/pages/publications/84973640322

U2 - 10.1016/j.poly.2016.04.029

DO - 10.1016/j.poly.2016.04.029

M3 - Article

AN - SCOPUS:84973640322

SN - 0277-5387

JO - Polyhedron

JF - Polyhedron

ER -

Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands

Abstract

Keywords

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CCDC 1470103: Experimental Crystal Structure Determination

CCDC 1470096: Experimental Crystal Structure Determination

CCDC 1470100: Experimental Crystal Structure Determination

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Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands

Abstract

Keywords

Access to Document

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Datasets

CCDC 1470103: Experimental Crystal Structure Determination

CCDC 1470096: Experimental Crystal Structure Determination

CCDC 1470100: Experimental Crystal Structure Determination

Cite this