期刊
INORGANIC CHEMISTRY
卷 59, 期 10, 页码 7067-7081出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c00538
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资金
- Indian Institute of Science (IISc), Bangalore, India
- Science & Engineering Research Board (SERB) [SRG/2019/000317]
- IISc
- Ministry of Human Resource Development (MHRD), Government of India [SG/MHRD-17-0014, SR/MHRD-17-0011]
- Council of Scientific & Industrial Research (CSIR), Government of India
- Department of Inorganic Chemistry, Palacky University Olomouc, Czech Republic
- project CEITEC 2020 [LQ1601]
- Ministry of Education, Youth and Sports of the Czech Republic
- Engineering and Physical Sciences Research Council (EPSRC) [EP/L018470/1]
- EPSRC National Electron Paramagnetic Resonance Facility and Service at the University of Manchester
- EPSRC [EP/L018470/1] Funding Source: UKRI
The three Co(II) complexes [Co(bbp)(2)][Co(NCS)(4)]center dot 4DMF (1), [Co(bbp)(NCS)2(DMF)]center dot 2DMF (2), and [Co(bbp)(NCS)(2)] (3) have been synthesized and characterized by single-crystal X-ray diffraction, magnetic, and various spectroscopic techniques. Complexes 1 and 3 are obtained by the reaction of Co(NCS) 2 with 2,6-bis(1H-benzo[d]imidazol-2-yl)pyridine (bbp), and complex 1 undergoes a structural transformation to form complex 2. A single-crystal X-ray study revealed that complex 1 is comprised of two Co(II) centers, a cationic octahedral Co(II) unit and an anionic tetrahedral Co(II) unit, while the Co(II) ion is in a distorted-octahedral environment in 2. Moreover, in complex 3, the Co(II) ion is in a distorted-square-pyramidal geometry. The effect of coordination geometry on the magnetic properties was studied by both static and dynamic magnetic measurements. Direct current (dc) magnetic susceptibility measurements showed that all of the Co(II) ions are in high-spin state in these complexes. Alternating current (ac) magnetic susceptibility measurements indicated that complexes 2 and 3 display slow relaxation of magnetization in an external dc magnetic field, while complex 1 displayed no such property. EPR experiments and theoretical calculations were consistent with the above findings.
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