Polynuclear manganese compounds have garnered interest as mimics and models of the water oxidizing complex (WOC) in photosystem II and as single molecule magnets. Molecular systems in which composition can be correlated to physical phenomena, such as magnetic exchange interactions, remain few primarily because of synthetic limitations. Here, we report the synthesis of a family of trimanganese(II) complexes of the type Mn₃X₃L (X = Cl^–, H^–, and MeO^–) where L^3– is a tris(β-diketiminate) cyclophane. The tri(chloride) complex (2) is structurally similar to the reported tri(bromide) complex (1) with the Mn₃X₃ core having a ladder-like arrangement of alternating M–X rungs, whereas the tri(μ-hydride) (3) and tri(μ-methoxide) (4) complexes contain planar hexagonal cores. The hydride and methoxide complexes are synthesized in good yield (48% and 56%) starting with the bromide complex employing a metathesis-like strategy. Compounds 2–4 were characterized by combustion analysis, X-ray crystallography, X-band EPR spectroscopy, SQUID magnetometry, and infrared and UV–visible spectroscopy. Magnetic susceptibility measurements indicate that the Mn₃ clusters in 2–4 are antiferromagnetically coupled, and the spin ground state of the compounds (S = 3/2 (1, 2) or S = 1/2 (3, 4)) is correlated to the identity of the bridging ligand and structural arrangement of the Mn₃X₃ core (X = Br, Cl, H, OCH₃). Electrochemical experiments on isobutyronitrile solutions of 3 and 4 display broad irreversible oxidations centered at 0.30 V.

中文翻译：

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将桥接配体与配体模板化的[Mn ^II ₃ X ₃ ] ³⁺簇的性质相关（X = Br ^–，Cl ^–，H ^–，MeO ^–）

多核锰化合物作为光系统II中水氧化复合物（WOC）的模拟物和模型以及作为单分子磁体而受到关注。主要由于合成的限制，其中组成可以与物理现象（例如磁交换相互作用）相关的分子系统仍然很少。在这里，我们报告了Mn ₃ X ₃ L（X = Cl ^–，H ^–和MeO ^–）型三聚体（II）配合物的合成，其中L ^3–是三（β-二酮）环烷。三（氯化物）配合物（2）在结构上类似于已报道的具有Mn的三（溴化物）配合物（1）₃ X _3的核呈梯形排列，交替排列M–X梯级，而三（μ-氢化物）（3）和三（μ-甲醇盐）（4）配合物包含平面六边形核。氢化物和甲醇盐的配合物从溴化物配合物开始，采用复分解样策略，合成产率高（分别为48％和56％）。化合物2 - 4通过燃烧分析，X射线晶体学，X波段EPR光谱，SQUID磁力和红外和紫外-可见光谱进行了表征。磁化率的测量表明，将Mn ₃簇2 - 4反铁磁性耦合，以及所述化合物的自旋基态（小号= 3/2（1，2）或小号= 1/2（3，4））相关联于Mn的桥连配体和结构布置的身份₃ X ₃芯（X = Br，Cl，H，OCH ₃）。在3和4的异丁腈溶液上进行的电化学实验显示，以0.30 V为中心的广泛不可逆氧化。