BIBLIOS

Document type
Journal articles

Document subtype
Full paper

Title
Experimental and Theoretical Studies on the Magnetic Properties of Manganese(II) Compounds with Mixed Isocyanate and Carboxylate Bridges

Participants in the publication
Yu Ma (Author)
Nuno A. G. Bandeira (Author)
Vincent Robert (Author)
En-Qing Gao (Author)

Summary
Abstract Two manganese(II) isocyanate complexes with different flexible zwitterionic dicarboxylate ligands, [Mn2(bcpp)(NCO)4]n (1; bcpp=1,3-bis(N-carboxylatomethyl-4-pyridinio)propane) and [Mn2(bcp)(NCO)4]n (2; bcp=bis(N-carboxylatomethyl)-4,4′-bipyridinium, have been synthesized and characterized by X-ray crystallography and magnetic measurements. Both compounds consist of two-dimensional coordination layers in which uniform anionic chains with mixed (NCO)2(COO) triple bridges are cross-linked by flexible cationic 4,4′-trimethylenedipyridinium spacers. Magnetic studies revealed antiferromagnetic interactions through the triple bridges (J=−8.0?cm−1 (1) and J=−8.6?cm−1 (2)), which are stronger than those in the isoelectronic analogue (N3)2(COO). To complement the experimental data, periodic and finite-cluster DFT and CASPT2 calculations were performed on the dimeric units of the (NCO)2(COO) and (N3)2(COO) mixed-bridged systems to support the Heisenberg picture and stress the relative efficiency of the magnetic couplers. It was found that the isocyanate ligand plays a greater role in the conveyance of antiferromagnetic behavior than the azide counterpart, and that both pseudohalide bridges function cooperatively with the carboxylate group.


Where published
Chemistry - A European Journal

Publication Identifiers
ISSN - 0947-6539

Publisher
Wiley



Document Identifiers
DOI - https://doi.org/10.1002/chem.201002243
URL - http://dx.doi.org/10.1002/chem.201002243

Rankings
SCIMAGO Q1 (2020) - 1.687 - Chemistry (miscellaneous)
Web Of Science Q2 (2020) - 5.236 - CHEMISTRY, MULTIDISCIPLINARY - SCIE