Mudoi Prashurya Pritam, Sarma Bipul, Choudhury Anup, Gogoi Nayanmoni
Department of Chemical Sciences, Tezpur University, Napaam 784028, Sonitpur, Assam, India.
Dalton Trans. 2021 Feb 14;50(6):2057-2066. doi: 10.1039/d0dt02826f. Epub 2021 Jan 22.
The possibility to induce intra-molecular metal-to-metal charge transfer in a cyanido bridged tetranuclear square shaped {FeNi} complex by employing protonation as an external stimulant is explored. Two cyanido bridged square shaped tetranuclear complexes, [{Ni(TPA)(μ-NC)Ni(CN)}]·4HO (2) and [{Ni(TPA)(μ-NC)Fe(bbp)(CN)}]·10HO (3) [TPA = tris(3,5-dimethylpyrazol-1-ylmethyl)amine and Hbbp = bis(2-benzimidazolyl)pyridine], are synthesized and characterized. Low temperature magnetic measurements reveal that complex 3 has dominant ferromagnetic interactions between low-spin Fe (S = 1/2) and high-spin Ni (S = 1) ions. UV-visible spectrophotometric measurements and electrochemical studies establish that reversible intra-molecular metal-to-metal electron transfer can be triggered in 3 upon the addition of either an acid or a base.
探索了通过使用质子化作为外部刺激剂在氰基桥联的四核方形{FeNi}配合物中诱导分子内金属到金属电荷转移的可能性。合成并表征了两种氰基桥联的方形四核配合物，[{Ni(TPA)(μ-NC)Ni(CN)}]·4H₂O (2) 和 [{Ni(TPA)(μ-NC)Fe(bbp)(CN)}]·10H₂O (3) [TPA = 三(3,5-二甲基吡唑-1-基甲基)胺，Hbbp = 双(2-苯并咪唑基)吡啶]。低温磁性测量表明，配合物3在低自旋Fe (S = 1/2) 和高自旋Ni (S = 1) 离子之间具有主要的铁磁相互作用。紫外可见分光光度测量和电化学研究表明，在加入酸或碱后，配合物3中可以触发可逆的分子内金属到金属电子转移。
