TY - JOUR
T1 - Syntheses and quadratic hyperpolarizabilities of some (pyridylalkynyl)metal complexes
T2 - Crystal structures of [Ni{2-(C≡C)C5H3NNO2-5}(PPh 3)(η-C5H5)], [Au{2-(C≡C)C5H3NNO2-5}(PPh3)] and [Au{2-(C≡C)C5H4N}(PPh3)]
AU - Naulty, Raina H.
AU - Cifuentes, Marie P.
AU - Humphrey, Mark G.
AU - Houbrechts, Stephan
AU - Boutton, Carlo
AU - Persoons, André
AU - Heath, Graham A.
AU - Hockless, David C.R.
AU - Luther-Davies, Barry
AU - Samoc, Marek
PY - 1997/11/21
Y1 - 1997/11/21
N2 - The complexes [Ru{2-(C≡C)C5H3NR-5}(PPh3) 2(η-C5H5)] (R = NO2 1 or H 2), [Ni{2-(C≡C)C5H3NR-5}(PPh3)-(η-C 5H5)] (R = NO23 or H 4) and [Au{2-(C≡C)C5H3NR-5}L] (L = PPh3, R = NO2 5 or H 6; L = PMe3, R = NO2 7) have been synthesized and 3, 5 and 6 structurally characterized; no significant increase in quinoidal vinylidene contribution to the acetylide ground-state structure is apparent on progression from structurally characterized phenylacetylide complexes to the new pyridylacetylide complexes, or upon replacement of 5-H by 5-NO2 in progressing from 6 to 5. The molecular quadratic optical non-linearities of 1-7 have been determined by hyper-Rayleigh scattering (HRS). The HRS measurements at 1064 nm are consistent with an increase in β upon replacement of phenyl by an N-heterocyclic ring (replacing a nitrophenylacetylide by a nitropyridylacetylide ligand) for the ruthenium and gold systems, but with no change for the nickel complexes, and with an increase in non-linearity upon replacement of PMe3 by PPh3 in progressing from 7 to 5. The bulk second-order susceptibilities of the series have been determined by Kurtz powder measurements at 1054 nm, with the only significant response (about eight times that of urea) being that of 3; this complex was the only one of the three structurally characterized to pack non-centrosymmetrically in the crystal lattice. Electrochemical data for 1-4 have been obtained; comparison to analogous nitrophenylacetlylide complexes reveals that replacing nitrophenylacetylide by nitropyridylacetylide leads to a significant increase in MII/III oxidation potential for the ruthenium complexes, but to no change for the nickel examples. The parameter EoMII/II -EoNO2/NO2 - was evaluated for 1-4, results for M = Ru vs. Ni being consistent with experimentally determined non-linearities, i.e. smaller ΔEo and larger non-linearities for ruthenium vs. nickel.
AB - The complexes [Ru{2-(C≡C)C5H3NR-5}(PPh3) 2(η-C5H5)] (R = NO2 1 or H 2), [Ni{2-(C≡C)C5H3NR-5}(PPh3)-(η-C 5H5)] (R = NO23 or H 4) and [Au{2-(C≡C)C5H3NR-5}L] (L = PPh3, R = NO2 5 or H 6; L = PMe3, R = NO2 7) have been synthesized and 3, 5 and 6 structurally characterized; no significant increase in quinoidal vinylidene contribution to the acetylide ground-state structure is apparent on progression from structurally characterized phenylacetylide complexes to the new pyridylacetylide complexes, or upon replacement of 5-H by 5-NO2 in progressing from 6 to 5. The molecular quadratic optical non-linearities of 1-7 have been determined by hyper-Rayleigh scattering (HRS). The HRS measurements at 1064 nm are consistent with an increase in β upon replacement of phenyl by an N-heterocyclic ring (replacing a nitrophenylacetylide by a nitropyridylacetylide ligand) for the ruthenium and gold systems, but with no change for the nickel complexes, and with an increase in non-linearity upon replacement of PMe3 by PPh3 in progressing from 7 to 5. The bulk second-order susceptibilities of the series have been determined by Kurtz powder measurements at 1054 nm, with the only significant response (about eight times that of urea) being that of 3; this complex was the only one of the three structurally characterized to pack non-centrosymmetrically in the crystal lattice. Electrochemical data for 1-4 have been obtained; comparison to analogous nitrophenylacetlylide complexes reveals that replacing nitrophenylacetylide by nitropyridylacetylide leads to a significant increase in MII/III oxidation potential for the ruthenium complexes, but to no change for the nickel examples. The parameter EoMII/II -EoNO2/NO2 - was evaluated for 1-4, results for M = Ru vs. Ni being consistent with experimentally determined non-linearities, i.e. smaller ΔEo and larger non-linearities for ruthenium vs. nickel.
UR - http://www.scopus.com/inward/record.url?scp=33748652965&partnerID=8YFLogxK
U2 - 10.1039/a702249b
DO - 10.1039/a702249b
M3 - Article
AN - SCOPUS:33748652965
SN - 0300-9246
SP - 4167
EP - 4174
JO - Journal of the Chemical Society - Dalton Transactions
JF - Journal of the Chemical Society - Dalton Transactions
IS - 22
ER -