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Organobimetallic Ru II -Re I 4-ethynylpyridyl complexes: structures and non-linear optical properties




Ge, Qingchun
Corkery, Timothy
Samoc, Marek
Hor, T S Andy
Humphrey, Mark

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Royal Society of Chemistry


A series of heterobimetallic complexes, [RuCp(CCpy-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(CCpy-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(CH 3CN)(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.



Keywords: Bidentate coordination mode; Cubic nonlinearities; Electrochemical studies; Hetero bimetallic complexes; Heterobimetallics; Heterometallic complexes; Metalloligands; Monomeric precursors; Non-linear optical properties; Pyridyl; Single crystal X-ray crysta



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