Bis(N-methylethylenediminesalicylaldiminato)iron(III) complexes. Magnetic, Moessbauer, and intersystem crossing rate studies in the solid and solution states for a new (S = /sup 1///sub 2/) in equilibrium (S = /sup 5///sub 2/) spin-equilibrium case
Bis(N-methylethylenediminesalicylaldiminato)iron(III) complexes. Magnetic, Moessbauer, and intersystem crossing rate studies in the solid and solution states for a new (S = /sup 1///sub 2/) in equilibrium (S = /sup 5///sub 2/) spin-equilibrium case
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双(N-甲基乙二胺水杨醛亚胺基)铁(III)络合物。
DOI：
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发表时间：
1978
期刊：
影响因子：
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通讯作者：
L. Wilson
中科院分区：
文献类型：
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作者：
R. Petty;E. Dose;M. Tweedle;L. Wilson
双(N-甲基乙二胺水杨醛二胺)铁(III)配合物，(Fe(X-Salmeen)/sub 2/)(PF/sub 6/)及其FeN/sub 4/O/sub 2/核已通过变温磁化率（10至300 K）和莫斯鲍尔光谱表明是新的（低自旋，S = /sup 1///sub 2/) 可逆（高自旋，S = /sup 5///sub 2/），固态自旋平衡化合物。根据穆斯堡尔谱，固态系统间窜越率的上限约为 10/sup 7/s/sup -1/。通过变温（200 至 300 K）磁化率和电子光谱测量验证，溶液状态下也支持自旋平衡。在解决方案中，激光拉曼温度跳跃动力学已被用来直接测量系间穿越的正向 (k/sub 1/) 和反向 (k/sub -1/) 速率常数，其中 2 x 10/sup 7/s/sup -1/ < 或大约 k < 或大约 2 x 10/sup 8/s/sup -1/。讨论了这些双三齿 (Fe/sup III/(X-Salmeen)/sub 2/)/sup +/ 配合物的系间交叉速率常数数据，并与电子相似（相同的 FeN/sub 4/O/sub 2/ 核）但结构不同（六齿配体）自旋平衡物质（Fe/sup III/(Sal)/sub 2/trien)/sup 的已有数据进行了比较 +/。 4 个表格、6 张图、40 篇参考文献。
Bis(N-methylethylenediaminesalicylaldiminato)iron(III) complexes, (Fe(X-Salmeen)/sub 2/)(PF/sub 6/), with their FeN/sub 4/O/sub 2/ cores have been shown by variable-temperature magnetic susceptibility (10 to 300 K) and Moessbauer spectroscopy to be new (low-spin, S = /sup 1///sub 2/) reversible (high-spin, S = /sup 5///sub 2/), spin-squilibrium compounds in the solid state. From the Moessbauer spectra, an upper limit of approximately 10/sup 7/s/sup -1/ has been established for the rate of intersystem crossing in the solid state. The spin equilibria are also supported in the solution state, as verified by variable-temperature (200 to 300 K) magnetic susceptibility and electronic spectroscopy measurements. In solution, laser Raman temperature-jump kinetics has been employed to directly measure the forward (k/sub 1/) and reverse (k/sub -1/) rate constants for the intersystem crossings with 2 x 10/sup 7/s/sup -1/ < or approximately k < or approximately 2 x 10/sup 8/s/sup -1/. Intersystem crossing rate constant data for these bis-tridentate (Fe/sup III/(X-Salmeen)/sub 2/)/sup +/ complexes are discussed and compared to data already available for the electronically similar (same FeN/sub 4/O/sub 2/ core) but structurally different (hexadentate ligand) spin-equilibrium species, (Fe/sup III/(Sal)/sub 2/trien)/sup +/. 4 tables, 6 figures, 40 references.