高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (10): 2128.doi: 10.7503/cjcu20190280

• 物理化学 • 上一篇    下一篇

异核反夹心配合物[M(AIP)](C5H5)[M'(AIP)](M, M'=V, Cr, Mn)潜在的自旋交叉和价态互变

刘楠楠1,*(),王建2   

  1. 1. 哈尔滨商业大学食品工程学院, 化学中心, 哈尔滨 150076
    2. 吉林大学理论化学研究所, 长春 130021
  • 收稿日期:2019-05-15 出版日期:2019-10-10 发布日期:2019-09-12
  • 通讯作者: 刘楠楠 E-mail:liunannyl@163.com
  • 基金资助:
    国家自然科学基金(No.21703049)

Potential Spin Crossover and Valence Tautomerism of Hetero-nuclear Inverse Sandwiches [M(AIP)](C5H5)[M'(AIP)](M, M'=V, Cr, Mn)

LIU Nannan1,*(),WANG Jian2   

  1. 1. Chemistry Center, College of Food Engineering, Harbin University of Commerce, Harbin 150076, China
    2. Institute of Theoretical Chemistry, Jilin University, Changchun 130021, China
  • Received:2019-05-15 Online:2019-10-10 Published:2019-09-12
  • Contact: LIU Nannan E-mail:liunannyl@163.com
  • Supported by:
    † Supported by the National Natural Science Foundation of China.(No.21703049)

摘要:

对反夹心体系[M(AIP)](C5H5)[M'(AIP)](M, M'=V, Cr, Mn; AIP=1-氨基-3-亚氨基-1-丙烯脱氢阴离子, C3N2 H 5 - )进行了理论研究. 结果表明, V-Cr体系存在五重态、 七重态和九重态的多稳态构型; Cr-Mn体系存在三重态、 五重态和七重态的多稳态构型. 在上述体系中, 金属原子的价态会随着异构体自旋态的不同而有所改变, V, Cr和Mn原子均可出现+1和+2价. 由于V-Cr和Cr-Mn体系一些双稳态构型间的自旋交叉能垒较低, 这使自旋交叉和价态互变过程变得可能. 解离能的研究结果表明, V-Cr体系解离能较大, 而Cr-Mn体系解离能略小, 两类体系均较稳定. [M(AIP)](C5H5)[M'(AIP)]存在自旋交叉和价态互变的可能性, 并具有较好的解离稳定性, 具有成为分子磁性材料的潜能.

关键词: 低价, Nacnac配体, 自旋多重度, 多稳态

Abstract:

The inverse sandwiches [M(AIP)](C5H5)[M'(AIP)](M, M'=V, Cr, Mn; AIP=dehydro-genated-1-amino-3-imino-prop-1-ene anion, C3N2 H 5 - ) were theoretically studied. The calculated results show that V-Cr system has the quintet, septet, and nonet multistable states; and Cr-Mn system has the triplet, quintet and septet multistable states. In these systems, the valence states of metal atoms vary with the spin states of isomers, the variable valence states of +1 and +2 could be observed in V, Cr and Mn atoms. Due to the low spin crossing barriers between some bistable states of V-Cr and Cr-Mn systems, the spin crossover and valence tautomerism become possible. Since [M(AIP)](C5H5)[M'(AIP)] not only performs the spin crossover and valence tautomerism, but also has the stability against dissociation, these molecules are potential candidate for molecular magnetic materials.

Key words: Low valent, Nacnac ligand, Spin multiplicity, Multistable state

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