Binuclear and trinuclear complexes of exoO(2)-cyclam

Vivienne A. White, Russell D. L. Johnstone, Keri L. McCall, Nicholas J. Long, Alexandra M. Z. Slawin, Neil Robertson

Research output: Contribution to journalArticlepeer-review

Abstract

Complexes of the ligand 2,3-dioxo-1,4,8,11-tetraaza-cyclotetradecane (exoO(2)-cyclam) have been prepared of formula [M-1{M-2(exoO(2)-cyclam)}(2)][BPh4](2) where (MM2)-M-1 = CoCo (3), ZnZn (4), MnCu (5), FeCu (6), CoCu (7), NiCu (8), ZnCu ( 9), and [(bipy)(2)Ru{Cu(exoO(2)-cyclam)}][NO3](2) (10). Complex 10 crystallised in the space group C2/c and shows Jahn-Teller distorted Cu(II) with axial nitrate ligands. The {Cu(exoO(2)-cyclam)} moiety chelates to the Ru with Ru-O distances of 2.082(5) angstrom. Complexes 5-10 show a Cu( II)/Cu(III) redox process and additional metal-centred (6, 8, 10) processes and ligand-centred (10) processes. The electrochemical and UV-Vis spectroelectrochemical study of 10 suggested two closely-spaced oxidations based on the Cu and Ru centres which suggests that substituted derivatives of 10 will be of interest for enhanced charge separation in dye-sensitised solar cells. Magnetic susceptibility measurements revealed dominant antiferromagnetic coupling within the trinuclear species 3, 5-8. Complex 10 showed Curie-Weiss behaviour with weak intermolecular interactions.

Original languageEnglish
Pages (from-to)2942-2948
Number of pages7
JournalDalton Transactions
Issue number27
DOIs
Publication statusPublished - 2007

Keywords / Materials (for Non-textual outputs)

  • MAGNETIC-PROPERTIES
  • CRYSTAL-STRUCTURE
  • MACROCYCLIC OXAMIDE
  • METAL-COMPLEXES
  • COPPER(II) COMPLEXES
  • COPPER(II)-NICKEL(II) COMPLEXES
  • LIGANDS
  • IONS
  • CU
  • OXAMIDE=1,4,8,11-TETRAAZACYCLOTRADECANNE-2,3-DIONE

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