Issue 42, 2021

Single-molecule magnets within polyoxometalate-based frameworks

Abstract

As an extension of our interest in polyoxometalates (POMs) and lanthanoids, we report the design and synthesis of two polyoxometalate-based frameworks under hydrothermal conditions; [Ho4(PDA)4(H2O)11][(SiO4)@W12O36]·8H2O (1) and [Tb4(PDA)4(H2O)12][(SiO4)@W12O36]·4H2O (2) (H2PDA = 1,10-phenanthroline-2,9-dicarboxylic acid). Both hybrids have been characterized by elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and powder/single-crystal X-ray diffraction. According to the structural analysis, 1 and 2 consist of 2D-cationic coordination polymers based on the respective lanthanoids and PDA2− as well as Keggin anions that reside in the interspaces between two adjacent layers as discrete counterions connected by extensive hydrogen bonding. Although the overall structures of 1 and 2 are composed of cationic and anionic layers, there are many differences in the cationic layers such as various coordination modes of PDA2−, different void shapes, and the existence of dinuclear Tb(III) units only in 2. Frameworks 1 and 2 were further characterized by dc and ac magnetic measurements and both exhibit slow relaxation of magnetization at low temperatures under an applied dc field. Their single-molecule magnet (SMM) properties are investigated, where weak field-induced SMM behaviour is observed at low temperatures in dynamic magnetic studies.

Graphical abstract: Single-molecule magnets within polyoxometalate-based frameworks

Supplementary files

Article information

Article type
Paper
Submitted
26 May 2021
Accepted
16 Sep 2021
First published
16 Sep 2021

Dalton Trans., 2021,50, 15047-15056

Single-molecule magnets within polyoxometalate-based frameworks

M. Babaei Zarch, M. Mirzaei, M. Bazargan, S. K. Gupta, F. Meyer and J. T. Mague, Dalton Trans., 2021, 50, 15047 DOI: 10.1039/D1DT01708J

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