4.7 Article

MnII and CoII Coordination Polymers Showing Field-Dependent Magnetism and Slow Magnetic Relaxation Behavior

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CRYSTAL GROWTH & DESIGN
卷 17, 期 8, 页码 4393-4404

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AMER CHEMICAL SOC
DOI: 10.1021/acs.cgd.7b00696

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  1. Israel Science Foundation [108/12]

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Four new Mn-II- and Co-II-containing magnetic coordination polymers, [{Mn(Br-isa)(bpe)center dot 1/2H(2)O}(n) (1), (Co(Br-isa)(bpe)(1.5)center dot 1/2H(2)O}n (2), [{Mn(Br-isa)(4-bpmh)}(4)center dot 6H(2)O](n) (3), and [{Co(Br-isa)(4-bpmh)}(2)center dot 21/2H(2)O](n) (4)] [isa = isophthalic acid, bpe = 1,2-bis-(4-pyridyl)ethylene and 4-bpmh = N,N'-bispyridine-4-yl-methylene-hydrazine], have been synthesized at room temperature, using 5-bromo isophthalic acid (Br-H(2)isa) and two different N-donating ancillary ligands. The complexes have been characterized by single-crystal X-ray diffraction and other physicochemical techniques. Structure determination reveals two-dimensional (2D) coordination network architectures for all the complexes. In 1, 3, and 4, Mn-II and Co-II dinuclear units are connected via Br-H(2)isa ligands to form infinite 1D chains. The ancillary N,N'-donor spacer ligands interconnect the 1D chains into 2D coordination layers. Complex 2, on the other hand, can be viewed as being composed of cationic [{Co(bpe)}4](8+) square units that are joined by anionic Br-isa(2-) bridges into a 2D gridlike framework. Topology analysis shows an sql/Shubnikov tetragonal plane-net topology for complexes 1, 3, and 4, and an SP 2-periodic net (4, 4) Ia topology for complex 2. Complexes 1 and 3 show a field-dependent change in magnetic behavior which is confirmed from the susceptibility measurements at varying fields, field-dependent magnetization measurements, as well as from hysteresis data. Complex 2 exhibits a slow magnetization relaxation phenomenon manifested by the AC susceptibility measurements at different temperatures and frequencies. Finally, complex 4 exhibits a magnetic feature that can be interpreted as antiferromagnetic exchange interactions between two syn-syn carboxylate-bridged Co-II atoms.

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