A soluble cyanide-bridged {Fe 4 Ni 4 } box encapsulating a Cs + ion: synthesis, structure and electronic properties
A soluble cyanide-bridged {Fe 4 Ni 4 } box encapsulating a Cs + ion: synthesis, structure and electronic properties
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封装 Cs 离子的可溶性氰化物桥联 {Fe 4 Ni 4 } 盒：合成、结构和电子性质
DOI：
10.1080/00958972.2018.1442575
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发表时间：
2018
影响因子：
1.9
通讯作者：
Lescouëzec, Rodrigue
中科院分区：
文献类型：
--
作者：
Plamont, Remi;Tami, Jessica;Jimenez, Juan-Ramon;Benchohra, Amina;Khaled, Omar;Gontard, Geoffrey;Li, Yanling;Lescouëzec, Rodrigue
氰化物配位团簇因其电子和磁性能而受到人们的关注。在这里，我们合成了一种新型的包覆Cs+的八金属氰化物盒。阳离子配合物Cs∧[FeIII4(Tp)4NiII4(NMe2Tp)4(μ-CN)12]+结晶为BF4−盐，其结构表明铯离子与十二个氰化物边相互作用。核磁共振光谱、质谱和循环伏安实验表明，这些相互作用可能是导致超分子组装的显著稳定性的原因，它在溶液中保持完整性。1的1h NMR谱显示出良好的分辨率信号，由于笼的顺磁性，这些信号被强烈地移位。被包裹的铯离子也受到顺磁笼的影响，显示出强烈的133c顺磁核磁共振信号。{Fe4Ni4}盒子具有显著的氧化还原灵活性，具有5种可达的氧化态，对应于4种FeIII/ feiions的可逆氧化/还原。四个连续氧化还原波的分离解释了金属离子之间通过氰化物桥的有效电子通信的发生。如磁性能所示，氰化物桥还能有效地传递铁和镍离子之间的铁磁相互作用。
Cyanide coordination clusters have received attention for their electronic and magnetic properties. Here, we synthesized a new octametallic cyanide box encapsulating a Cs+. The cationic complex Cs⊂[FeIII4(Tp)4NiII4(NMe2Tp)4(μ-CN)12]+was crystallized as a BF4−salt and its structure reveals that the cesium ion interacts with the twelve cyanide edges. These interactions are likely responsible for the remarkable stability of the supramolecular assembly, which maintains its integrity in solution, as shown by NMR spectroscopy, mass spectrometry, and cyclic voltammetry experiments. The1H NMR spectrum of1shows well-resolved signals, which are strongly shifted due to the paramagnetic nature of the cage. The encapsulated caesium ion is also affected by the paramagnetic cage and shows a strongly shifted133Cs paramagnetic NMR signal. The {Fe4Ni4} box shows remarkable redox flexibility with five accessible oxidation states, which correspond to the reversible oxidation/reduction of the four FeIII/FeIIions. The separation of the four consecutive redox waves accounts for the occurrence of an efficient electronic communication between the metal ions through the cyanide bridges. The cyanide bridges are also efficient in transmitting a ferromagnetic interaction between the iron and nickel ions as shown by the magnetic properties.