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Coordination polymers from a highly flexible alkyldiamine-derived ligand: structure, magnetism and gas adsorption studiesElectronic supplementary information (ESI) available: Additional magnetism plots, additional figures, X-ray powder diffraction data, thermogravimetric analysis plots, CO2 isotherms for 2 and 3, N2 isotherm data for 4, CO2 isotherm fitting data for 4, table of hydrogen bonding parameters, 1H and 13C NMR spectra for Me4L and H4L. CCDC 1406627-1406631. For ESI and crystallographi
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 H 4 L derived from 1,2-diaminoethane have been examined. The compound poly-[Ni 3 ( HL ) 2 (O...
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| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
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| Summary: | 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
H
4
L
derived from 1,2-diaminoethane have been examined. The compound poly-[Ni
3
(
HL
)
2
(OH
2
)
4
]·2DMF·2H
2
O
1
, a two-dimensional coordination polymer, contains aqua- and carboxylato-bridged trinuclear Ni
II
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-[Zn
2
L
]·2DMF·3H
2
O
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-[Zn
2
(
L
)(DMSO)
4
]·3DMSO·3H
2
O
3
, a highly solvated two-dimensional coordination polymer, displayed poor stability characteristics, however a structurally related material poly-[Zn
2
(
L
)(
bpe
)(DMSO)
2
]·DMSO·3H
2
O
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 CO
2
over N
2
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.
Studies into a series of coordination polymers from a new diamine polycarboxylate ligand reveal an interplay between flexibility and material properties. |
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| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c5dt02323h |