Continuing our work on the structural and magnetic aspects of the one-dimensional (1-D) coordination polymers of the [M(pmdc)(H2O)2]·H2O kind (M Fe, Co, Ni, Cu, Zn; pmdc pyrimidine-4,6-dicarboxylate), we have combined ab initio X-ray powder diffraction methods with in situ thermodiffractometry and thermal analyses to characterize the selective and reversible transformation of the [M(pmdc)(H2O)2]·H2O compounds (M Fe, Co, Ni, Cu) into the bis-hydrated [M(pmdc)(H2O)2] counterparts by moderate heating, which is followed by an irreversible transformation into two-dimensional (2-D) anhydrous species. The structural features of the transient bis-hydrated species and of the completely dehydrated one are described for M Cu. Remarkably, the ﬁrst dehydration process does not alter the 1-D nature of the [M(pmdc)(H2O)2] chains; on the contrary, the second dehydration gives rise to the loss of the axially coordinated water molecules with a concomitant condensation of the 1-D chains into 2-D layers through ancillary carboxylate bridging groups. The magnetic properties of the anhydrous [M(pmdc)] species (M Co, Ni, Cu) have been investigated, showing that these phases behave as 1-D antiferromagnets with interchain interactions. Notably, in the case of the [Ni(pmdc)] system, a weak ferromagnetic ordering, arising from a spin canting phenomenon with a blocking temperature of 13 K, is observed.
|Data di pubblicazione:||2009|
|Titolo:||Thermally induced interconversions of metal-pyrimidine-4,6-dicarboxylate polymers: A structural, spectroscopic, and magnetic study|
|Digital Object Identifier (DOI):||10.1021/ic802365w|
|Codice identificativo ISI:||WOS:000264759500046|
|Codice identificativo Scopus:||2-s2.0-64349088110|
|Codice identificativo Pubmed:||19281181|
|Appare nelle tipologie:||Articolo su Rivista|