TY - JOUR
T1 - Organobimetallic RuII-ReI 4-ethynylpyridyl complexes
T2 - Structures and non-linear optical properties
AU - Ge, Qingchun
AU - Corkery, T. Christopher
AU - Humphrey, Mark G.
AU - Samoc, Marek
AU - Hor, T. S.Andy
PY - 2009
Y1 - 2009
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=68149106079&partnerID=8YFLogxK
U2 - 10.1039/b902800e
DO - 10.1039/b902800e
M3 - Article
SN - 1477-9226
SP - 6192
EP - 6200
JO - Dalton Transactions
JF - Dalton Transactions
IS - 31
ER -