Incorporating Highly Anisotropic Four-Coordinate Co(II) Ions within One-Dimensional Coordination Chains

Singh, Saurabh Kumar (2023) Incorporating Highly Anisotropic Four-Coordinate Co(II) Ions within One-Dimensional Coordination Chains. Crystal Growth & Design, 23 (4). pp. 2980-2987. ISSN 1528-7483

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Abstract

Low-coordinate metallic ions have been well recognized for constructing good-performance single ion magnets (SIMs) due to their enhanced magnetic anisotropy; however, the incorporation of such specific ions into coordination polymers is still challenging. Here, we reported two new CoII coordination polymers, namely [Co(pdms)(bpe)]n (1) and {[Co(pdms)(tpb)]·H2O·tpb}n (2) (H2pdms = 1,2-bis(methanesulfonamido)benzene, bpe = 1,2-di(4-pyridyl)ethane, tpb = 1,2,4,5-tetra(4-pyridyl)benzene). Single crystal X-ray diffraction experiments indicated that the CoII centers in both 1 and 2 display a distorted tetrahedral geometry with quasi C2v symmetry and are linked into a one-dimensional (1D) zig-zag chain via the ditopic bridging ligand of bpe in 1 while a ribbon chain via the tetradentate linker of tpb in 2. Magnetic studies revealed the easy-axis magnetic anisotropy of the CoII ions with different zero-field splitting D of −19 cm-1 (1) and −33 cm-1 (2), likely due to the distinct changes in the Npy-Co-Npy bite angles (100.20° (1) vs. 93.90° (2)). Moreover, slow magnetic relaxation proceeded via different relaxation mechanisms under applied dc fields was observed, giving an effective energy barrier (Ueff) of 69.6 K for 1 and 76.6 K for 2, respectively. The ab initio calculations on both the polymers further confirmed the sign and magnitude of the ZFS parameters and nicely reproduced the experimental results. Our study demonstrated a great potential for applying the well-studied and highly anisotropic 4-coordinate metal ions within a coordination polymer, opening a viable means to tuning magnetic anisotropy via topological control.

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IITH Creators:

IITH Creators	ORCiD
Singh, Saurabh Kumar	http://www.orcid.org/0000-0001-9488-8036

Item Type:

Article

Uncontrolled Keywords:

Magnetic anisotropy; Coordination chains; Coordination Polymers; Coordination-polymers; Metallic ions; One-dimensional; Performance; Pyridyl; Single ion; Specific ions; X- ray diffractions; Benzene; Cobalt compounds; Crystal symmetry; Metal ions; Microchannels; Single crystals

Subjects:

Chemistry
Chemistry > Inorganic chemistry

Divisions:

Department of Chemistry

Depositing User:

Mr Nigam Prasad Bisoyi

Date Deposited:

13 Sep 2023 07:08

Last Modified:

13 Sep 2023 07:08

URI:

http://raiithold.iith.ac.in/id/eprint/11676