多酸辅助氰根桥连异金属配合物的合成及磁性研究

氰根桥连金属配合物在分子磁学领域具有重要地位。氰根（C≡N^–）具有强的电、磁传递能力，通过构筑块策略和原子替代原则可实现对目标分子结构和功能的系统调控，展现出在构筑高磁有序温度的分子磁体、分子纳米磁体、自旋翻转及电子转移光磁分子材料等方面的优势。然而，由于其线性配位特点的限制，氰根桥连配合物在结构多样性方面仍显不足。本论文选择具有较高的分子对称性、较大尺寸以及可变的电荷等特性的多酸阴离子为辅助，基于三氰合铁构筑基元（[(Tp^R)Fe(CN)₃]^–）和3d过渡金属体系，探索一种新的合成策略，开发具有不同维度、不同结构特点及磁性特征的氰根桥连配合物。

通过引入Keggin型的磷钼酸根[PMo₁₂O₄₀]^3–，合成了一系列零维的具有不同结构特点的氰根桥连配合物：平面四方结构的[Fe₂Co₂]（1），互嵌式双三角双锥结构的[Fe₃Co₃]（2），立方体结构的[Fe₄Co₄]（3），六棱柱结构的[Fe₆Co₆]（4）及底心四方结构的[Fe₈Co₆]（5）。其中配合物2、4及5的金属氰根骨架均未被报道过，说明多酸阴离子的引入对于构筑多样且新颖的氰根桥连簇合物具有显著影响。另外，配合物3表现出不完全的热致和光致电子转移行为，转变温度为225 K，光激发亚稳态可维持在200 K。

选取不同的多酸阴离子，辅助构建了一系列具有“珍珠链”结构的一维链状配合物6–11。在已知的链状氰根桥连配合物中，该结构并不常见，但理论上其结构特征有利于单链磁体的构筑。此外，在质子型溶剂中得到了带状配合物12，其主体骨架是由三角双锥分子簇构成的一维分子链。带的宽度达到了约3 nm，是目前晶体学表征的最宽一维配位聚合配合物，展示了构建介于一维和二维之间的维度交叉配合物的潜力。结果表明，配合物6、8和10–12都具有单链磁体行为，其中多酸阴离子充当磁稀释剂，最大限度地减小链间的相互作用。

以硅钨酸[SiW₁₂O₄₀]^4–（缩写为SiW₁₂）为模板，成功构建了两例电中性的氰根桥连二维蜂窝状配合物{SiW₁₂@Fe^III₂M^II₃}（M = Ni, 13; Fe, 14）。其中硅钨酸阴离子处在每个蜂窝中心，与周围六个M金属中心通过配位键相连。配合物13和14为反铁磁体，有序温度分别为9.8和15.5 K。进一步实现对配合物14中Fe^II离子的抗磁掺杂，得到不同Fe^II:Zn^II比例的配合物15–18，其磁性从长程有序转为缓慢磁弛豫。配合物16（掺杂比例为2:1）表现出典型的单链磁体行为，有效能垒为46.3 K。此外，配合物13通过加热可实现单晶到单晶的转变，得到配合物19。结构中的甲醇分子被置换成水分子，改变了层与层之间的堆积方式，其磁性研究表现为铁磁有序。多酸在构建高稳定性氰根桥连二维材料中起着重要作用，且此类二维材料在磁学特性上具有可调控性。

Cyanometalates play an important role in the field of molecular magnetism. The cyanide bridges (C≡N^–) enable efficient magnetic exchange and electron transfer. The directional synthesis and structural regulation of cyanometalates are achievable through the building block method and atomic substitution principle. Therefore, the cyanide bridges show good potential in constructing high-temperature molecular magnets, molecule-based nanomagnets, spin crossover complexes, electron transfer materials, and opto-magnetism compounds. However, due to the rigidity of its linear coordination characteristics, only a limited amount of model compounds were reported. In this thesis, the polyoxometalates with high molecular symmetry, bulky structure, and variable charge were employed to assist the synthesis of cyanometalates in tricyanoiron building units ([(Tp^R)Fe(CN)₃]^–) and 3d transition metals system. As a result, three series of cyanide-bridged complexes with different dimensions and structural characteristics were achieved.

A series of zero-dimensional cyanometalates bearing polyoxometalates were obtained by introducing Keggin-type [PMo₁₂O₄₀]^3– under different reaction conditions: [Fe₂Co₂] (1) with square structure; [Fe₃Co₃] (2) with two mutually perpendicular trigonal bipyramids(TBP) structure; [Fe₄Co₄] (3) with cubic structure; [Fe₆Co₆] (4) with hexagonal prism cluster; [Fe₈Co₆] (5) with bottom-centered tetragonal cluster. Among them, the topology of complexes 2, 4, and 5 have not been reported in cyanometalates indicating that the introduction of polyoxoanions has a significant impact on the construction of diverse cyanometalates. Compound 3 exhibited incomplete thermal and photo-induced electron transfer, with a transition temperature of 225 K and a photoexcited metastable state below 200 K.

By introducing different polyoxoanions, a series of one-dimensional chains 6–11 containing "pearl-chain" structure were synthesized. Among the known one-dimensional cyanometalates, the "pearl-chain" structure is rare, but it is theoretically advantageous for the construction of high-performance single-chain magnets. In addition, a complex tape-like compound 12 was successfully synthesized in protic solvent. The main skeleton of compound 12 is composed of TBP modules. This tape is approximately 3 nm in width, among the widest one-dimensional coordination assemblies, demonstrating the potential for constructing dimensional-crossover complexes between one-dimension and two-dimension. Compounds 6, 8 and 10–12 show single-chain magnet (SCM) behavior, in which polyoxoanions act as magnetic diluents to minimize chain-to-chain interactions.

Two charge-neutral cyanide bridged two-dimensional honeycomb-like compounds {SiW₁₂@Fe^III₂M^II₃} (M = Ni, 13; Fe, 14) were successfully constructed by using [SiW₁₂O₄₀]^4– as template. Compounds 13 and 14 are antiferromagnets, with ordered temperatures of 9.8 and 15.5 K, respectively. By diamagnetic doping to compound 14, compounds 15–18 with different Fe^II:Zn^II ratio were obtained, and the magnetic properties changed from long-range ordered to slow magnetic relaxation. Compound 16 with a doping ratio of 2:1 (Fe^II:Zn^II) shows a single chain magnet behavior with an effective energy barrier of 46.3 K. In addition, compound 19 could be obtained by heating compound 13 in a single-crystal to single-crystal transformation manner. Water molecules replaced all the methanol molecules in the structure, and the interlayer packing mode changed. As a result, compound 19 exhibits ferromagnetic rather than antiferromagnetic ordering. Polyoxometalates play an important role in the construction of cyanide bridged two-dimensional materials with high-stability, and these two-dimensional materials are tunable in terms of magnetic properties.

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