Tuning chain topologies and magnetic anisotropy in one-dimensional cobalt( ii ) coordination polymers via distinct dicarboxylates

Based on a terpyridine derivative and two different dicarboxylate ligands, two new cobalt( ii ) coordination polymers, namely [Co(pytpy)(DClbdc)] n (1) and [Co(pytpy)(ndc)] n (2) ( pytpy = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine, H 2 DClbc = 2,5-dichloroterephthalic acid, and H 2 ndc = 2,6-naphthalen...

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Published in:CrystEngComm 2022-05, Vol.24 (21), p.3928-3937
Main Authors: Tian, Zhengfang, Moorthy, Shruti, Xiang, Huan, Peng, Peng, You, Maolin, Zhang, Qian, Yang, Shun-Yi, Zhang, Yang-Lu, Wu, Dong-Qing, Singh, Saurabh Kumar, Shao, Dong
Format: Article
Language:English
Subjects:
Anisotropy
Cobalt
Coordination polymers
Crystal structure
Crystals
Low temperature
Magnetic anisotropy
Magnetic induction
Magnetic relaxation
Polymers
Single crystals
Topology
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Summary:Based on a terpyridine derivative and two different dicarboxylate ligands, two new cobalt( ii ) coordination polymers, namely [Co(pytpy)(DClbdc)] n (1) and [Co(pytpy)(ndc)] n (2) ( pytpy = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine, H 2 DClbc = 2,5-dichloroterephthalic acid, and H 2 ndc = 2,6-naphthalenedicarboxylic acid), were hydrothermally synthesized and characterized structurally and magnetically. Single-crystal X-ray diffraction revealed that 1 and 2 are one-dimensional (1D) linear and zigzag chain complexes, respectively, with the Co 2+ centers located in a compressed and an elongated bipyramid of 1 and 2, respectively. Magnetic investigation revealed that the chain complexes exhibit distinct easy-axis and easy-plane magnetic anisotropy with D = −95.6 and −42.8 cm −1 for 1 and 2, respectively. The inverse magnetic anisotropy of 1 and 2 was further confirmed and understood using ab initio calculations. Interestingly, field-induced single-ion magnet (SIM) behaviors were evidenced at low temperatures with the effective energy barrier of U eff = 27.3 and 12.7 cm −1 for 1 and 2, respectively. The foregoing results provide not only a way for the construction of 1D cobalt( ii ) coordination polymers with slow magnetic relaxation behavior but also a chance to tune chain topologies and magnetic anisotropy in one-dimensional coordination polymers via different dicarboxylates.
ISSN:1466-8033
1466-8033
DOI:10.1039/D2CE00437B