Redox active ferrocenyl appended pyridinediimine-ligated multifunctional cobalt(II) complexes: prospective compounds for spin-crossover and anticancer applications

IF 5.9 3区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Communications Pub Date : 2026-04-01 Epub Date: 2026-02-13 DOI:10.1016/j.inoche.2026.116342

Rishikumar I. Patel , Uma Iyer , Elias Mosaffa , Debraj Chakraborty , Debopam Sarkar , Kaila R. Rahbarnoohi , Ferman A. Chavez , Enrique Colacio , María Mar Quesada-Moreno , Neeraj Jain , Atanu Banerjee

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Abstract

Two redox-active cobalt(II) complexes, [Co(PDI-Fc₂)₂](ClO₄)₂ (1) and [Co(PDI-Fc₂)₂][CoCl₄] (2), derived from a ferrocenyl-pyridinediimine ligand (PDI-Fc₂) were synthesized and characterized. Single-crystal X-ray studies reveal that both complexes feature low spin cobalt(II) in distorted octahedral coordination environment, derived from bis-tridendate PDI-Fc₂ (−[Co^II(Fc₂-PDI)₂]²⁺). Complex 1 has perchlorate anions and acetonitrile as the solvent of crystallization, while complex 2 has anionic cobalt tetrachloride [CoCl₄]²⁻ as the counter ion. Magnetic measurements demonstrate that both complexes 1 and 2 are in a low-spin state under ambient conditions and exhibit thermally induced spin-crossover characteristics. In addition, complex 1 display slow relaxation of magnetization in an external DC magnetic field indicative of single-molecule magnet (SMM) behaviour, whereas complex 2 displayed no such characteristics. Electrochemical studies reveal the redox-active nature of both the ligand and complexes. DFT studies were performed to elucidate the electronic structure of 1 and 2. The free Schiff base ligand and both of the complexes exhibit significant cytotoxicity against the ovarian cancer cell line (PA1) with an IC₅₀ range of 7–16 μM, while showing lower toxicity towards the normal McCoy cell line. Hoechst-propidium iodide (Hoechst-PI) staining and reactive oxygen species (ROS) assays confirm the induction of apoptosis mediated by oxidative stress. The results render these Cobalt-Schiff-base complexes as promising candidates as both multifunctional materials and selective anticancer agents.

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氧化还原活性二茂铁附加吡啶二亚胺连接多功能钴（II）配合物：具有自旋交叉和抗癌应用前景的化合物

由二茂铁基吡啶二亚胺配体（PDI-Fc2）合成了两个具有氧化还原活性的钴（II）配合物[Co(PDI-Fc2)2](ClO4)2(1)和[Co(PDI-Fc2)2][CoCl4](2)。单晶x射线研究表明，这两种配合物都具有畸变八面体配位环境下的低自旋钴（II），来源于双三叉戟PDI-Fc2（−[CoII(Fc2-PDI)2]2+）。配合物1以高氯酸盐阴离子和乙腈为结晶溶剂，配合物2以阴离子四氯化钴[CoCl₄]2−为反离子。磁测量表明，配合物1和2在环境条件下均处于低自旋状态，并表现出热诱导自旋交叉特性。此外，配合物1在外部直流磁场中表现出缓慢的磁化弛豫，表明单分子磁铁（SMM）的行为，而配合物2则没有这种特征。电化学研究揭示了配体和配合物的氧化还原活性。用DFT研究了1和2的电子结构。游离希夫碱配体和两种复合物对卵巢癌细胞系PA1具有显著的细胞毒性，IC50范围为7 ~ 16 μM，而对正常McCoy细胞系的毒性较低。hoechst -丙啶碘化（Hoechst-PI）染色和活性氧（ROS）测定证实氧化应激介导的细胞凋亡。结果表明这些钴-希夫碱配合物是多功能材料和选择性抗癌剂的有希望的候选者。

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来源期刊

Inorganic Chemistry Communications 化学-无机化学与核化学

CiteScore

5.50

自引率

7.90%

发文量

1013

审稿时长

53 days

期刊介绍： Launched in January 1998, Inorganic Chemistry Communications is an international journal dedicated to the rapid publication of short communications in the major areas of inorganic, organometallic and supramolecular chemistry. Topics include synthetic and reaction chemistry, kinetics and mechanisms of reactions, bioinorganic chemistry, photochemistry and the use of metal and organometallic compounds in stoichiometric and catalytic synthesis or organic compounds.