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Spin crossover in 2D iron(ii) phthalazine cyanometallic complexes.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-04-28 , DOI: 10.1039/d0dt00783h Volodymyr M Hiiuk 1 , Sergiu Shova 2 , Aurelian Rotaru 3 , Alexander A Golub 4 , Igor O Fritsky 5 , Il'ya A Gural'skiy 5
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-04-28 , DOI: 10.1039/d0dt00783h Volodymyr M Hiiuk 1 , Sergiu Shova 2 , Aurelian Rotaru 3 , Alexander A Golub 4 , Igor O Fritsky 5 , Il'ya A Gural'skiy 5
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Two new 2D spin-crossover (SCO) analogues of Hofmann clathrates of composition [Fe(phth)2MII(CN)4] (where phth = phthalazine; MII = Pd, Pt) have been synthesized and their structures and switchable behaviour have been characterized. Single-crystal X-ray analysis reveals that the Pt and Pd derivatives contain FeII centres equatorially surrounded by four equivalent μ4-[MII(CN)4]2- groups. Two crystallographically equivalent phthalazine (phth) ligands occupy the axial positions of each FeII site, completing its octahedral coordination environment. The stabilization of these structures is realized via supramolecular C-HM interactions and π-π stacking. Temperature-dependent magnetic susceptibility measurements showed that Pt (T1/2↓ = 211 K and T1/2↑ = 218 K) and Pd (T1/2↓ = 202 K and T1/2↑ = 207 K) derivatives display cooperative spin crossover with narrow thermal hysteresis loops. In addition, spin crossover in these complexes was characterized by optical measurements, differential scanning calorimetry, and IR and Raman spectroscopy. This research shows that the use of phthalazine leads to the production of new SCO systems with attractive transition characteristics and opens up new perspectives for the design of switchable complexes based on fused bicyclic azine ligands.
中文翻译：
2D铁（ii）酞嗪氰金属络合物的自旋交叉。
合成了组成[Fe（phth）2MII（CN）4]的霍夫曼包合物的两个新的二维自旋交叠（SCO）类似物（其中phth =邻苯二甲酰胺； MII = Pd，Pt），并已表征了它们的结构和可转换行为。X射线单晶分析表明，Pt和Pd衍生物的FeII中心被四个等价的μ4-[MII（CN）4] 2-基包围。两个结晶学上等效的酞嗪（phth）配体占据每个FeII位点的轴向位置，从而完成了其八面体配位环境。这些结构的稳定是通过超分子C-HM相互作用和π-π堆积实现的。温度相关的磁化率测量结果表明，Pt（T1 / 2↓= 211 K和T1 / 2↑= 218 K）和Pd（T1 / 2↓= 202 K和T1 / 2↑= 207 K）衍生物表现出协同自旋交叉具有较窄的热滞回线。此外，这些配合物中的自旋交叉通过光学测量，差示扫描量热法以及IR和拉曼光谱学来表征。这项研究表明，使用酞嗪可以产生具有有吸引力的过渡特性的新型SCO系统，并为设计基于稠合双环嗪配体的可转换配合物开辟了新的前景。
更新日期：2020-03-24
中文翻译：
2D铁（ii）酞嗪氰金属络合物的自旋交叉。
合成了组成[Fe（phth）2MII（CN）4]的霍夫曼包合物的两个新的二维自旋交叠（SCO）类似物（其中phth =邻苯二甲酰胺； MII = Pd，Pt），并已表征了它们的结构和可转换行为。X射线单晶分析表明，Pt和Pd衍生物的FeII中心被四个等价的μ4-[MII（CN）4] 2-基包围。两个结晶学上等效的酞嗪（phth）配体占据每个FeII位点的轴向位置，从而完成了其八面体配位环境。这些结构的稳定是通过超分子C-HM相互作用和π-π堆积实现的。温度相关的磁化率测量结果表明，Pt（T1 / 2↓= 211 K和T1 / 2↑= 218 K）和Pd（T1 / 2↓= 202 K和T1 / 2↑= 207 K）衍生物表现出协同自旋交叉具有较窄的热滞回线。此外，这些配合物中的自旋交叉通过光学测量，差示扫描量热法以及IR和拉曼光谱学来表征。这项研究表明，使用酞嗪可以产生具有有吸引力的过渡特性的新型SCO系统，并为设计基于稠合双环嗪配体的可转换配合物开辟了新的前景。
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