TY - JOUR
T1 - Organometallic complexes for nonlinear optics. 43. Quadratic optical nonlinearities of dipolar alkynylruthenium complexes with phenyleneethynylene/ phenylenevinylene bridges
AU - Rigamonti, Luca
AU - Babgi, Bandar
AU - Cifuentes, Marie P.
AU - Roberts, Rachel L.
AU - Petrie, Simon
AU - Stranger, Robert
AU - Righetto, Stefania
AU - Teshome, Ayele
AU - Asselberghs, Inge
AU - Clays, Koen
AU - Humphrey, Mark G.
PY - 2009/4/20
Y1 - 2009/4/20
N2 - The syntheses of trans-[Ru(4,4′-C≡CC6H 4C≡CC6H4NO2)Cl(dppe) 2] (19) and the systematically varied complexes trans-[Ru(4,4′, 4′′-C≡CC6H4X2C 6H4Y2C6H4NO 2)Cl(L2)2] [L2 = dppe, X2 = C≡C, Y2 = (E)-CH=CH (12), C≡C (18); L2 = dppe, X2 = (E)-CH)CH, Y2 = C≡C (14), (E)-CH)CH (16); L2 = dppm, X2 = C≡C, Y2 = (E)-CH)CH (13); L2 = dppm, X2 = (E)-CH=CH, Y2 = C≡C (15), (E)-CH)CH (17)] are reported, the latter being donorbridge- acceptor complexes varying in bridge composition by replacement of yne with E-ene linkages, together with their cyclic voltammetric data, linear optical, and quadratic nonlinear optical response data. RuII/III oxidation potentials increase on replacing yne linkage by E-ene linkage at the phenylene adjacent to the metal center, and on replacing dppe by dppm co-ligands. The low-energy optical absorption maxima occur in the region 20400-23300 cm -1 and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon π-bridge lengthening by addition of phenyleneethynylene units, and on replacing E-ene linkages by yne linkages. Time-dependent density functional theory calculations on model complexes have suggested assignments for the low-energy bands. The optical spectra of selected oxidized species contain low-energy ligand-to-metal charge transfer (LMCT) bands centered in the region 9760-11800 cm-1. Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected β0 value on π-bridge lengthening, a trend that is not seen with β values because of the blue-shift in λmax for this structural modification. Replacing yne linkages by E-ene linkage at the phenylene adjacent to the metal center or dppm co-ligand by dppe results in an increase in β and β0 values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced secondharmonic generation (EFISH) studies at 1907 nm do not afford clear trends.
AB - The syntheses of trans-[Ru(4,4′-C≡CC6H 4C≡CC6H4NO2)Cl(dppe) 2] (19) and the systematically varied complexes trans-[Ru(4,4′, 4′′-C≡CC6H4X2C 6H4Y2C6H4NO 2)Cl(L2)2] [L2 = dppe, X2 = C≡C, Y2 = (E)-CH=CH (12), C≡C (18); L2 = dppe, X2 = (E)-CH)CH, Y2 = C≡C (14), (E)-CH)CH (16); L2 = dppm, X2 = C≡C, Y2 = (E)-CH)CH (13); L2 = dppm, X2 = (E)-CH=CH, Y2 = C≡C (15), (E)-CH)CH (17)] are reported, the latter being donorbridge- acceptor complexes varying in bridge composition by replacement of yne with E-ene linkages, together with their cyclic voltammetric data, linear optical, and quadratic nonlinear optical response data. RuII/III oxidation potentials increase on replacing yne linkage by E-ene linkage at the phenylene adjacent to the metal center, and on replacing dppe by dppm co-ligands. The low-energy optical absorption maxima occur in the region 20400-23300 cm -1 and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon π-bridge lengthening by addition of phenyleneethynylene units, and on replacing E-ene linkages by yne linkages. Time-dependent density functional theory calculations on model complexes have suggested assignments for the low-energy bands. The optical spectra of selected oxidized species contain low-energy ligand-to-metal charge transfer (LMCT) bands centered in the region 9760-11800 cm-1. Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected β0 value on π-bridge lengthening, a trend that is not seen with β values because of the blue-shift in λmax for this structural modification. Replacing yne linkages by E-ene linkage at the phenylene adjacent to the metal center or dppm co-ligand by dppe results in an increase in β and β0 values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced secondharmonic generation (EFISH) studies at 1907 nm do not afford clear trends.
UR - http://www.scopus.com/inward/record.url?scp=65349173064&partnerID=8YFLogxK
U2 - 10.1021/ic801953z
DO - 10.1021/ic801953z
M3 - Article
SN - 0020-1669
VL - 48
SP - 3562
EP - 3572
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 8
ER -