Long-range electronic coupling in bis(cyclometalated) ruthenium complexes

C. Patoux, J.P. Launay, M. Beley, S. Chodorowski-Kimmes, J.P. Collin, Stuart James, J.P. Sauvage

Research output: Contribution to journalArticlepeer-review

163 Citations (Scopus)

Abstract

Symmetrical and unsymmetrical ligands containing terpyridyl coordinating units (N, N, N) or a cyclometalating equivalent (N, C, N), connected back-to-back either directly or via a p-terphenylene or 1,3-phenylene spacer, have been used to construct new diruthenium complexes. These compounds incorporate various terdentate chelates as capping ligands, to allow a double control of the electronic properties of each subcomplex and of the ensemble: via the terminal ligand or through the bridging fragment. Electronic coupling was studied from the intervalence transitions observed in several bimetallic ruthenium complexes of the bis-(cyclometalated) type differing by the substitution of a nitrogen atom by carbon in the terminal terpyridyl unit. The largest metal-metal interaction was found in complexes for which the terminal complexing unit is of the 1,3-di-2-pyridylbenzene type, i.e., with the carbon atom located on the metal-metal C-2 axis of the molecule. Investigations of the mechanism of interaction by extended Huckel calculations showed that the replacement of nitrogen by carbon raises the filled ligand levels, increasing the mixing with ligand orbitals and thus the metal-metal coupling. Finally, the intervalence transition was still observed for a bridging ligand containing three phenylene units as spacers, corresponding to a 24-Angstrom metal-metal distance.
Original languageEnglish
Pages (from-to)3717-3725
Number of pages9
JournalJournal of the American Chemical Society
Volume120
Issue number15
Publication statusPublished - 22 Apr 1998

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Long-range electronic coupling in bis(cyclometalated) ruthenium complexes'. Together they form a unique fingerprint.

Cite this