Field-induced slow magnetic relaxation behaviours in binuclear cobalt(ii) metallocycles and exchange-coupled clusters

Shao, Dong and Moorthy, Shruti and Zhou, Yue and Wu, Si-Tong and Zhu, Jing-Yan and Yang, Jiong and Wu, Dong-Qing and Tian, Zhengfang and Singh, Saurabh Kumar (2022) Field-induced slow magnetic relaxation behaviours in binuclear cobalt(ii) metallocycles and exchange-coupled clusters. Dalton Transactions, 51 (24). pp. 9357-9368. ISSN 1477-9226

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Abstract

Precise control of the structures and magnetic properties of a molecular material constitutes an important challenge to realize tailor-made magnetic function. Herein, we report that the ligand-directed coordination self-assembly of a dianionic cobalt(ii) mononuclear complex and selective organic linkers has led to two distinct dicobalt(ii) complexes, [Co2(pdms)2(bpym)3]·2MeCN (1) and [Co(pdms)(bipm)]2·3DMF (2) (H2pdms = 1,2-bis(methanesulfonamide)benzene; bpym = 2,2′-bipyrimidine; bimp = 1,4-bis[(1H-imidazol-1-yl)methyl]benzene). Structural analyses revealed that complexes 1 and 2 are discrete binuclear molecules containing two neutral {Co(pdms)} species bridged by bpym and bimp ligands, respectively, forming an exchange-coupled CoII2 dimer and a rare CoII2 metallocycle. Magnetic studies found that 1 exhibits considerable antiferromagnetic interactions transferred by the bpym bridge while negligible magnetic interactions in 2 due to the long bimp ligands. Interestingly, both the complexes show significant magnetic anisotropy and thus exhibit slow magnetic relaxation under an external dc field originating from spin-lattice relaxation. Detailed theoretical calculations were further applied to understand the magnetic interactions and magnetic anisotropy in 1 and 2. The foregoing results highlight that coordination solids with programmed structures and magnetic properties can be designed and prepared through a judicious selection of molecular complex building blocks and organic linkers. © 2022 The Royal Society of Chemistry.

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IITH Creators:

IITH Creators	ORCiD
Singh, Saurabh Kumar	UNSPECIFIED

Item Type:

Article

Additional Information:

This work was supported by a start-up fund from Huanggang Normal University (No. 2042021033) and the Open Foundation of State Key Laboratory of Coordination Chemistry (No. SKLCC2208). SKS acknowledges the Department of Science and Technology for the Start-up Research Grant (SRG/2020/001323) and IIT Hyderabad for generous funding. SM acknowledges the Prime Minister Research Fellowship. The support and resources provided by PARAM Shivay Facility under the National Supercomputing Mission, Government of India at the Indian Institute of Technology, Varanasi, are gratefully acknowledged. DQW acknowledges the National Natural Science Foundation of China (No. 21901152).

Uncontrolled Keywords:

Binuclear cobalt; Coupled clusters; Exchange coupled; Field-induced; Magnetic interactions; Metallocycles; Organic linkers; Precise control; Relaxation behaviors; Slow magnetic relaxations

Subjects:

Chemistry

Divisions:

Department of Chemistry

Depositing User:

. LibTrainee 2021

Date Deposited:

13 Oct 2022 11:18

Last Modified:

13 Oct 2022 11:18

URI:

http://raiithold.iith.ac.in/id/eprint/10919