Spin-Crossover in a Pseudo-tetrahedral Bis(formazanate) Iron Complex

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• 作者：Raquel Travieso-Puente ; J. O. P. Broekman ; Mu-Chieh Chang ; Serhiy Demeshko ; Franc Meyer ; Edwin Otten
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：May 4, 2016
• 年：2016
• 卷：138
• 期：17
• 页码：5503-5506
• 全文大小：329K
• 年卷期：0
• ISSN：1520-5126

文摘

Spin-crossover in a pseudo-tetrahedral bis(formazanate) iron(II) complex (1) is described. Structural, magnetic, and spectroscopic analyses indicate that this compound undergoes thermal switching between an S=0 and an S=2 state, which is very rare in four-coordinate complexes. The transition to the high-spin state is accompanied by an increase in Fe–N bond lengths and a concomitant contraction of intraligand N–N bonds. The latter suggests that stabilization of the low-spin state is due to the π-acceptor properties of the ligand. One-electron reduction of 1 leads to the formation of the corresponding anion, which contains a low-spin (S=1/2) Fe(I) center. The findings are rationalized by electronic structure calculations using density functional theory.