Secondary metal coordination using a tetranuclear complex as ligand leading to hexanuclear complexes with enhanced thermal barriers for electron transfer

Shihao Liu, Yi Fei Deng, Zi Yi Chen, Lingyi Meng, Xiaoyong Chang, Zhiping Zheng, Yuan Zhu Zhang

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Postsynthesis of the paramagnetic square-shaped complex {[(Tp*Me)Fe(μ-CN)2(CN)][Co(dmbpy)2]}2 (BPh4)2·6MeCN·H2O [1, Tp*Me = tris(3,4,5-trimethylpyrazole)-borate; dmbpy = 4,4′-dimethyl-2,2′-bipyr-idine)] by grafting transition metal(II) thiocyanates via its terminal cyano groups afforded three hexanuclear [Fe2Co2M2] clusters (M = Zn, 2; Co, 3; Cd, 4). The peripheral metal-complex units serving as excellent electron acceptors were found to help stabilize the low-temperature state of FeII,LS-CoIII,LS within the complex core. As a result, the desolvated complexes 2-4 underwent reversible and sharp thermally induced electron-transfer behavior with the transition temperatures (T1/2) up to 312, 296, and 365 K, respectively, demonstrating an effective means of manipulating thermal barriers of the celebrated cyano-bridged square core.

Original languageEnglish (US)
Pages (from-to)2530-2538
Number of pages9
JournalCCS Chemistry
Volume3
Issue number9
DOIs
StatePublished - 2021
Externally publishedYes

Keywords

  • Cyanide
  • Electron transfer
  • Hexanuclear
  • Photomagnet
  • Postsynthesis
  • Square

ASJC Scopus subject areas

  • Chemistry(all)

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