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

Chris S Hawes, Nicholas F Chilton, Boujemaa Moubaraki, Gregory P Knowles, Alan L Chaffee, Keith S Murray, Stuart R Batten, David R Turner

    Research output: Contribution to journalArticlepeer-review


    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
    Issue number40
    Publication statusPublished - Oct 2015


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