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Issue 31, 2009
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Organobimetallic RuII–ReI4-ethynylpyridyl complexes: structures and non-linear optical properties

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Abstract

A series of heterobimetallic complexes, [RuCp(C[triple bond, length as m-dash]Cpy-4)(P-P)][Re(CO)3(N-N)]+ (P-P = dppf, N-N = bpy 5, Me2bpy 6, tBu2bpy 7, phen 8, tpy 9; P-P = 2PPh3, N-N = bpy 10) have been obtained from Lewis addition between the metalloligands [RuCp(C[triple bond, length as m-dash]Cpy-4)(P-P)] (P-P = dppf 1; 2PPh32) and solvent-stabilised fac-[Re(CH3CN)(CO)3(N-N)]+. All new complexes 5–10, together with fac-[ReBr(CO)3(tpy)] (3) and fac-[Re(CH3CN)(CO)3(tpy)][PF6] (4), are characterized by solution spectroscopy; 3 and 5–9 are also characterized by single-crystal X-ray crystallography. The terpyridine ligands in 3 and 9 are in an unusual η2-bidentate coordination mode with a pendant pyridyl. Electrochemical studies showed successive metal-based oxidations and a ligand-centered reduction in 5–10. Significant oxidation changes are observed at the Ru(II) and Re(I) centers in 5–10 when compared with their respective monometallic components. Cubic nonlinearities of 5–10 determined by the Z-scan technique at 750 nm reveal two-photon absorption that increases significantly on progression from Ru(II) monomeric precursors to heterobimetallics, suggesting NLO enhancement upon heterometallic complex formation.

Graphical abstract: Organobimetallic RuII–ReI4-ethynylpyridyl complexes: structures and non-linear optical properties

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Publication details

The article was received on 19 Feb 2009, accepted on 06 May 2009 and first published on 23 Jun 2009


Article type: Paper
DOI: 10.1039/B902800E
Citation: Dalton Trans., 2009,0, 6192-6200
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    Organobimetallic RuII–ReI4-ethynylpyridyl complexes: structures and non-linear optical properties

    Q. Ge, T. C. Corkery, M. G. Humphrey, M. Samoc and T. S. A. Hor, Dalton Trans., 2009, 0, 6192
    DOI: 10.1039/B902800E

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