Manganese‐Octacyanidoniobate‐Based Ferrimagnet Possessing Bridging Ligands with Disulfide Bonds
Manganese‐Octacyanidoniobate‐Based Ferrimagnet Possessing Bridging Ligands with Disulfide Bonds
复制标题
具有二硫键桥连配体的锰-八氰胺基亚铁磁体
DOI：
10.1002/ejic.202100747
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发表时间：
2021
影响因子：
2.3
通讯作者：
Ohkoshi Shin‐ichi
中科院分区：
文献类型：
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作者：
Kanno Takefumi;Nakabayashi Koji;Imoto Kenta;Ohkoshi Shin‐ichi
我们合成了一种氰基-桥接Mn - Nb金属组装体，具有具有二硫键的大尺寸桥接配体，[Mn(dpds)2]2[Nb(CN)8]⋅6H2O （MnNb, dpds: 4,4′-双吡啶二硫）。mnnb具有三维配位框架，其中Mn和Nb位点由氰化物桥接，而Mn位点由dds配体结合。两种晶体独立的dds配体在二硫键周围弯曲，具有较大的C（吡啶）−S−S−C（吡啶）二面角，分别为105.4(5)°和102.2(5)°。对于分子基磁体，dpds是一个相对较大的桥接配体，但由于其弯曲结构，它与氰基桥接Mn - Nb配位框架的有限空间兼容。此外，MnII（S=5/2,g=2）和NbIV（S=1/2,g=2）在mnnbof−13 cm−1的反铁磁耦合产生了临界温度为46 K的铁磁。
We synthesized a cyanido‐bridged Mn−Nb metal assembly possessing large‐sized bridging ligands with disulfide bonds, [Mn(dpds)2]2[Nb(CN)8] ⋅ 6H2O (MnNb, dpds: 4,4’‐dipyridyldisulfide).MnNbhas a three‐dimensional coordination framework in which the Mn and Nb sites are bridged by cyanides, while the Mn sites are combined by dpds ligands. The two crystallographically independent dpds ligands are bent around the disulfide bond with large C(pyridine)−S−S−C(pyridine) dihedral angles of 105.4(5)° and 102.2(5)°, respectively. For molecule‐based magnets, dpds is a relatively large bridging ligand, but it is compatible with the limited space of the cyanido‐bridged Mn−Nb coordination framework due to the bent structure. Additionally, antiferromagnetic coupling inMnNbof −13 cm−1between MnII(S=5/2,g=2) and NbIV(S=1/2,g=2) induces ferrimagnetism with a critical temperature of 46 K.