Obtaining nanosized, solution-processable molecules and ions with switchable magnetic moments is crucial for the development of storage devices. In this work, two seven-nuclear rhenium cluster complexes Cs₇[{Re₃S₄(CN)₉}{Re₄S₄}(CN)₉]·10H₂O (1) and K₇[{Re₃Se₄(CN)₉}{Re₄Se₄}(CN)₉]·15H₂O (2) were prepared and comprehensively characterized. The obtained clusters with an even number of cluster valence electrons (CVE) are found to consist of triangular and tetrahedral fragments strongly bonded together by bridging inner ligands and constitute a new structural type. Magnetochemical analysis of complexes has revealed the presence of non-magnetic singlet (M_S = 0) and magnetic doublet (M_S = ±1) states with a temperature-dependent population. These states, according to DFT calculations, may originate from the zero-field splitted S = 1 ground state, which is quite surprising given that clusters with an even number of CVE usually possess low-spin states (S = 0) due to the delocalized nature of the frontier molecular orbitals (MOs) and the effective removal of MO degeneracy by Jahn–Teller spatial distortion of the clusters. We have also succeeded in controlling one-electron oxidation of the clusters, which results in an odd number of CVE and drives the compound into a conventional paramagnetic S = 1/2 state.

中文翻译：

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多自旋超原子：具有不寻常磁性的七核铼簇


获得纳米级、可溶液加工的分子和具有可切换磁矩的离子对于存储设备的开发至关重要。在这项工作中，两个七核铼簇配合物 Cs₇[{Re₃S₄（CN）₉}{Re₄S₄}（CN）₉]·10H₂O （1） 和 K₇[{Re₃Se₄（CN）₉}{Re₄制备了 Se₄}（CN）₉]·15H₂O （2） 并进行了综合表征。发现获得的具有偶数个簇价电子 （CVE） 的簇由三角形和四面体片段组成，这些片段通过桥接内部配体紧密结合在一起，并构成一种新的结构类型。配合物的磁化学分析揭示了非磁性单重态 （M_S = 0） 和磁双重态 （M_S = ±1） 的存在，这些状态具有温度依赖性种群。根据 DFT 的计算，这些状态可能源自零场分裂的 S = 1 基态，这非常令人惊讶，因为具有偶数个 CVE 的簇通常具有低自旋态 （S = 0），因为前沿分子轨道 （MO） 的离域性质和通过簇的 Jahn-Teller 空间扭曲有效去除了 MO 简并性。 我们还成功地控制了团簇的单电子氧化，这导致了奇数个 CVE，并将化合物驱动到常规的顺磁性 S = 1/2 状态。