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Synthesis, electrochemical and photophysical properties of heterodinuclear Ru-Mn and Ru-Zn complexes bearing ambident Schiff base ligand

Dalton Transactions, ISSN: 1477-9234, Vol: 39, Issue: 24, Page: 5650-5657
2010
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While ruthenium tris(diimine) complexes have been extensively studied, this is not the case with ruthenium bis(diimine)X complexes where X represents a pyridinyl-based ligand. The synthesis of a new complex ([2][PF ]) bearing two ambident Schiff base ligands (HL) constituted by the assembly of phenol and pyridinyl moieties is reported. Thanks to the heteroditopic property of HL, compound [2] was used as an original metalloligand for the coordination of a redox-active (Mn(iii)) and redox-inactive (Zn(ii)) second metal cation affording three heterodinuclear complexes, namely, [(bpy)RuLMn(acac)][PF ] ([3][PF]; acac = acetylacetonate), [(bpy)RuLMn(OAc)][PF] ([4][PF], OAc = acetate), and [(bpy) RuLZn][PF] ([5][PF ]). The influence of the second metal with regard to the photophysical and electrochemical properties of the ruthenium bis(diimine)X subunit was then investigated. In the case of Ru(ii)-Mn(iii) heterodinuclear complexes, a partial quenching of the luminescence was observed as a consequence of an efficient electron transfer process from the ruthenium to the manganese. EPR and spectrophotometric analyses of the oxidized species resulting from the one-electron oxidation of compounds [3] and [4] showed the formation of a Mn(iv) species for [3] and an organic free radical for [4]. © 2010 The Royal Society of Chemistry.

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