Coordination polymers from a highly flexible alkyldiamine-derived ligand: structure, magnetism and gas adsorption studies

Chris Samuel Hawes, Nicholas Frederick Chilton, Boujemaa Moubaraki, Gregory Paul Knowles, Alan Loyd Chaffee, Keith Spencer Murray, Stuart Robert Batten, David Roger Turner

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The synthesis and structural, magnetic and gas adsorption properties of a series of coordination polymer materials prepared from a new, highly flexible and internally functional tetrakis-carboxybenzyl ligand H4L derived from 1,2-diaminoethane have been examined. The compound poly-[Ni3(HL)2(OH2)4]·2DMF·2H2O 1, a two-dimensional coordination polymer, contains aqua- and carboxylato-bridged trinuclear NiII clusters, the magnetic behaviour of which can be well described through experimental fitting and ab initio modelling to a ferromagnetically coupled trimer with a positive axial zero-field splitting parameter D. Compound poly-[Zn2L]·2DMF·3H2O 2, a three-dimensional coordination polymer displaying frl topology, contains large and well-defined solvent channels, which are shown to collapse on solvent exchange or drying. Compound poly-[Zn2(L)(DMSO)4]·3DMSO·3H2O 3, a highly solvated two-dimensional coordination polymer, displayed poor stability characteristics, however a structurally related material poly-[Zn2(L)(bpe)(DMSO)2]·DMSO·3H2O 4 was prepared under similar synthetic conditions by including the 1,2-bis(4-pyridyl)ethylene bpe co-ligand. Compound 4, containing small one-dimensional solvent channels, shows excellent structural resilience to solvent exchange and evacuation, and the evacuated material displays selective adsorption of CO2 over N2 at 273 K in the pressure range 0–1 atm. Each of the coordination polymers displays subtle differences in the conformation and binding mode of the ligand species, with switching between two distinct conformers (X-shaped and H-shaped), as well as a variable protonation state of the central core, with significant effects on the resulting network structures and physical properties of the materials.
Original languageEnglish
Pages (from-to)17494-17507
Number of pages14
JournalDalton Transactions
Volume44
Issue number40
DOIs
Publication statusPublished - 2015

Cite this

@article{cbb7a73538134362b615f89079018e27,
title = "Coordination polymers from a highly flexible alkyldiamine-derived ligand: structure, magnetism and gas adsorption studies",
abstract = "The synthesis and structural, magnetic and gas adsorption properties of a series of coordination polymer materials prepared from a new, highly flexible and internally functional tetrakis-carboxybenzyl ligand H4L derived from 1,2-diaminoethane have been examined. The compound poly-[Ni3(HL)2(OH2)4]·2DMF·2H2O 1, a two-dimensional coordination polymer, contains aqua- and carboxylato-bridged trinuclear NiII clusters, the magnetic behaviour of which can be well described through experimental fitting and ab initio modelling to a ferromagnetically coupled trimer with a positive axial zero-field splitting parameter D. Compound poly-[Zn2L]·2DMF·3H2O 2, a three-dimensional coordination polymer displaying frl topology, contains large and well-defined solvent channels, which are shown to collapse on solvent exchange or drying. Compound poly-[Zn2(L)(DMSO)4]·3DMSO·3H2O 3, a highly solvated two-dimensional coordination polymer, displayed poor stability characteristics, however a structurally related material poly-[Zn2(L)(bpe)(DMSO)2]·DMSO·3H2O 4 was prepared under similar synthetic conditions by including the 1,2-bis(4-pyridyl)ethylene bpe co-ligand. Compound 4, containing small one-dimensional solvent channels, shows excellent structural resilience to solvent exchange and evacuation, and the evacuated material displays selective adsorption of CO2 over N2 at 273 K in the pressure range 0–1 atm. Each of the coordination polymers displays subtle differences in the conformation and binding mode of the ligand species, with switching between two distinct conformers (X-shaped and H-shaped), as well as a variable protonation state of the central core, with significant effects on the resulting network structures and physical properties of the materials.",
author = "Hawes, {Chris Samuel} and Chilton, {Nicholas Frederick} and Boujemaa Moubaraki and Knowles, {Gregory Paul} and Chaffee, {Alan Loyd} and Murray, {Keith Spencer} and Batten, {Stuart Robert} and Turner, {David Roger}",
year = "2015",
doi = "10.1039/c5dt02323h",
language = "English",
volume = "44",
pages = "17494--17507",
journal = "Journal of the Chemical Society. Dalton Transactions",
issn = "1477-9226",
publisher = "The Royal Society of Chemistry",
number = "40",

}

Coordination polymers from a highly flexible alkyldiamine-derived ligand: structure, magnetism and gas adsorption studies. / Hawes, Chris Samuel; Chilton, Nicholas Frederick; Moubaraki, Boujemaa; Knowles, Gregory Paul; Chaffee, Alan Loyd; Murray, Keith Spencer; Batten, Stuart Robert; Turner, David Roger.

In: Dalton Transactions, Vol. 44, No. 40, 2015, p. 17494-17507.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Coordination polymers from a highly flexible alkyldiamine-derived ligand: structure, magnetism and gas adsorption studies

AU - Hawes, Chris Samuel

AU - Chilton, Nicholas Frederick

AU - Moubaraki, Boujemaa

AU - Knowles, Gregory Paul

AU - Chaffee, Alan Loyd

AU - Murray, Keith Spencer

AU - Batten, Stuart Robert

AU - Turner, David Roger

PY - 2015

Y1 - 2015

N2 - The synthesis and structural, magnetic and gas adsorption properties of a series of coordination polymer materials prepared from a new, highly flexible and internally functional tetrakis-carboxybenzyl ligand H4L derived from 1,2-diaminoethane have been examined. The compound poly-[Ni3(HL)2(OH2)4]·2DMF·2H2O 1, a two-dimensional coordination polymer, contains aqua- and carboxylato-bridged trinuclear NiII clusters, the magnetic behaviour of which can be well described through experimental fitting and ab initio modelling to a ferromagnetically coupled trimer with a positive axial zero-field splitting parameter D. Compound poly-[Zn2L]·2DMF·3H2O 2, a three-dimensional coordination polymer displaying frl topology, contains large and well-defined solvent channels, which are shown to collapse on solvent exchange or drying. Compound poly-[Zn2(L)(DMSO)4]·3DMSO·3H2O 3, a highly solvated two-dimensional coordination polymer, displayed poor stability characteristics, however a structurally related material poly-[Zn2(L)(bpe)(DMSO)2]·DMSO·3H2O 4 was prepared under similar synthetic conditions by including the 1,2-bis(4-pyridyl)ethylene bpe co-ligand. Compound 4, containing small one-dimensional solvent channels, shows excellent structural resilience to solvent exchange and evacuation, and the evacuated material displays selective adsorption of CO2 over N2 at 273 K in the pressure range 0–1 atm. Each of the coordination polymers displays subtle differences in the conformation and binding mode of the ligand species, with switching between two distinct conformers (X-shaped and H-shaped), as well as a variable protonation state of the central core, with significant effects on the resulting network structures and physical properties of the materials.

AB - The synthesis and structural, magnetic and gas adsorption properties of a series of coordination polymer materials prepared from a new, highly flexible and internally functional tetrakis-carboxybenzyl ligand H4L derived from 1,2-diaminoethane have been examined. The compound poly-[Ni3(HL)2(OH2)4]·2DMF·2H2O 1, a two-dimensional coordination polymer, contains aqua- and carboxylato-bridged trinuclear NiII clusters, the magnetic behaviour of which can be well described through experimental fitting and ab initio modelling to a ferromagnetically coupled trimer with a positive axial zero-field splitting parameter D. Compound poly-[Zn2L]·2DMF·3H2O 2, a three-dimensional coordination polymer displaying frl topology, contains large and well-defined solvent channels, which are shown to collapse on solvent exchange or drying. Compound poly-[Zn2(L)(DMSO)4]·3DMSO·3H2O 3, a highly solvated two-dimensional coordination polymer, displayed poor stability characteristics, however a structurally related material poly-[Zn2(L)(bpe)(DMSO)2]·DMSO·3H2O 4 was prepared under similar synthetic conditions by including the 1,2-bis(4-pyridyl)ethylene bpe co-ligand. Compound 4, containing small one-dimensional solvent channels, shows excellent structural resilience to solvent exchange and evacuation, and the evacuated material displays selective adsorption of CO2 over N2 at 273 K in the pressure range 0–1 atm. Each of the coordination polymers displays subtle differences in the conformation and binding mode of the ligand species, with switching between two distinct conformers (X-shaped and H-shaped), as well as a variable protonation state of the central core, with significant effects on the resulting network structures and physical properties of the materials.

UR - http://pubs.rsc.org.ezproxy.lib.monash.edu.au/en/content/articlepdf/2015/dt/c5dt02323h

U2 - 10.1039/c5dt02323h

DO - 10.1039/c5dt02323h

M3 - Article

VL - 44

SP - 17494

EP - 17507

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

SN - 1477-9226

IS - 40

ER -