Kowalkowska-Zedler Daria, Nedelko Natalia, Kazimierczuk Katarzyna, Aleshkevych Pavlo, Łyszczek Renata, Ślawska-Waniewska Anna, Pladzyk Agnieszka
Department of Inorganic Chemistry, Faculty of Chemistry, Gdańsk University of Technology Narutowicza Str. 11/12 80-233 Gdańsk Poland
Institute of Physics, Polish Academy of Sciences Aleja Lotników 32/46 02-668 Warsaw Poland.
RSC Adv. 2020 Aug 6;10(49):29100-29108. doi: 10.1039/d0ra06036d. eCollection 2020 Aug 5.
Three heteroleptic complexes of Co(ii) tri--butoxysilanethiolates have been synthesized with piperidine [Co{SSi(OBu)}(ppd)] 1, piperazine Co{SSi(OBu)}(NH)·2CHCN 2, and -ethylimidazole [Co{SSi(OBu)}(etim)] 3. The complexes have been characterized by a single-crystal X-ray, revealing their tetrahedral geometry on Co(ii) coordinated by two nitrogen and two sulfur atoms. Complexes 1 and 3 are mononuclear, whereas 2 is binuclear. The spectral properties and thermal properties of 1-3 complexes were established by FTIR spectroscopy for solid samples and TGA. The magnetic properties of complexes 1, 2, and 3 have been investigated by static magnetic measurements and X-band EPR spectroscopy. These studies have shown that 1 and 3, regardless of the similarity in structure of CoNS cores, demonstrate different types of local magnetic anisotropy. Magnetic investigations of 2 reveal the presence of weak antiferromagnetic intra-molecular Co(ii)-Co(ii) interactions that are strongly influenced by the local magnetic anisotropy of individual Co(ii) ions.
已合成了三种钴（II）三叔丁氧基硅烷硫醇盐的异核配合物，分别是与哌啶形成的[Co{SSi(OBu)}(ppd)] 1、与哌嗪形成的Co{SSi(OBu)}(NH)·2CHCN 2以及与N-乙基咪唑形成的[Co{SSi(OBu)}(etim)] 3。通过单晶X射线对这些配合物进行了表征，揭示了钴（II）由两个氮原子和两个硫原子配位形成的四面体几何结构。配合物1和3是单核的，而配合物2是双核的。通过对固体样品进行傅里叶变换红外光谱（FTIR）和热重分析（TGA）确定了配合物1 - 3的光谱性质和热性质。通过静态磁性测量和X波段电子顺磁共振光谱（X-band EPR）研究了配合物1、2和3的磁性。这些研究表明，尽管配合物1和3的CoNS核结构相似，但表现出不同类型的局域磁各向异性。对配合物2的磁性研究揭示了存在弱的反铁磁分子内Co（II）-Co（II）相互作用，这种相互作用受到单个Co（II）离子的局域磁各向异性的强烈影响。
