A simple methodology for constructing ferromagnetically coupled Cr(iii) compounds

Hector W. L. Fraser, Lucy Smythe, Sourav Dey, Gary S. Nichol, Stergios Piligkos, Gopalan Rajaraman, Euan K. Brechin

Research output: Contribution to journalArticlepeer-review

Abstract

A large family of chromium(iii) dimers has been synthesised and magneto-structurally characterised using a combination of carboxylate and diethanolamine type ligands. The compounds have the general formula [Cr-2(R-1-deaH)(2)(O2CR2)Cl-2]Cl where R-1 = Me and R-2 = H (1), Me (2), CMe3 (3), Ph (4), 3,5-(Cl)(2)Ph (5), (Me)(5)Ph (6), R-1 = Et and R-2 = H (7), Ph (8). The compound [Cr-2(Me-deaH)(2)Cl-4] (9) was synthesised in order to study the effect of removing/adding the carboxylate bridge on the observed magnetic behaviour. Direct current (DC) magnetic susceptibility measurements showed ferromagnetic (FM) exchange interactions between the Cr(iii) centres in the carboxylate bridged family with coupling constants in the range +0.37 <J <+8.02 cm(-1). Removal of the carboxylate to produce the dialkoxide-bridged compound 9 resulted in antiferromagnetic (AFM) exchange between the Cr(iii) ions. DFT calculations reveal the ferromagnetic exchange is the result of an orbital counter-complementarity effect occuring upon introduction of the bridging carboxylate.

Original languageEnglish
Pages (from-to)8100-8109
Number of pages10
JournalDalton Transactions
Volume47
Issue number24
Early online date30 May 2018
DOIs
Publication statusPublished - 28 Jun 2018

Keywords

  • SINGLE-MOLECULE MAGNET
  • GAUSSIAN-BASIS SETS
  • ORBITAL COMPLEMENTARITY
  • CHROMIUM(III) COMPLEX
  • COPPER(II) COMPLEXES
  • EXCHANGE INTERACTION
  • GROUND-STATE
  • ATOMS LI
  • CR-III
  • WHEELS

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