TY - JOUR
T1 - Organometallic complexes for non-linear optics. 51. second- and third-order non-linear optical properties of alkynylgold complexes
AU - Barlow, Adam
AU - Babgi, Bandar
AU - Samoc, Marek
AU - Corkery, T. Christopher
AU - Van Cleuvenbergen, Stijn
AU - Asselberghs, Inge
AU - Clays, Koen
AU - Cifuentes, Marie P.
AU - Humphrey, Mark G.
PY - 2012
Y1 - 2012
N2 - The alkynes HC≡CC 6H 2-2,6-Et 2-4- C≡CC 6H 4-4-NO 2 (4) and HC≡CC 6H 4-4-C≡CC 6H 2-2,6-Et 2-4-C≡CC 6H 4-4-NO 2 (6) and gold alkynyl complexes Au{C≡CC 6H 2-2,5-(OEt) 2-4-C≡CC 6H 4-4-NO 2}(PPh 3) (7), Au(C≡CC 6H 2-2,6-Et 2-4-C≡CC 6H 4-4-NO 2)(PPh 3) (8), and Au(C≡CC 6H 4-4-C≡CC 6H 2-2,6-Et 2-4-C≡CC 6H 4-4-NO 2)(PPh 3) (9) have been synthesized. The linear optical properties and quadratic optical non-linearities of 79 have been measured, the latter by hyper-Rayleigh scattering at 1064nm, and compared with data for the previously reported complexes Au(C≡CC 6H 4-4-NO 2)(PPh 3) (10) and Au(C≡CC 6H 4-4-C≡CC 6H 4-4-NO 2)(PPh 3) (11). The optical absorption maximum red-shifts and the first hyperpolarizabilities increase on -system lengthening and on introduction of electron-releasing substituents on the -bridge ring adjacent to the metal centre. The cubic non-linear optical properties of 1,4-{(PCy 3)Au(C≡C)} 2C 6H 4 (12) and {(PCy 3)Au(C≡C-4-C 6H 4C≡C)} 6C 6 (13) have been assessed by wide spectroscopic range femtosecond Z-scan studies; the maximal values of the imaginary component and the effective two-photon absorption cross-section increase markedly on proceeding from linear complex 12 to 6-fold-symmetric complex 13, an increase that is maintained when data are scaled by relative molecular weight.
AB - The alkynes HC≡CC 6H 2-2,6-Et 2-4- C≡CC 6H 4-4-NO 2 (4) and HC≡CC 6H 4-4-C≡CC 6H 2-2,6-Et 2-4-C≡CC 6H 4-4-NO 2 (6) and gold alkynyl complexes Au{C≡CC 6H 2-2,5-(OEt) 2-4-C≡CC 6H 4-4-NO 2}(PPh 3) (7), Au(C≡CC 6H 2-2,6-Et 2-4-C≡CC 6H 4-4-NO 2)(PPh 3) (8), and Au(C≡CC 6H 4-4-C≡CC 6H 2-2,6-Et 2-4-C≡CC 6H 4-4-NO 2)(PPh 3) (9) have been synthesized. The linear optical properties and quadratic optical non-linearities of 79 have been measured, the latter by hyper-Rayleigh scattering at 1064nm, and compared with data for the previously reported complexes Au(C≡CC 6H 4-4-NO 2)(PPh 3) (10) and Au(C≡CC 6H 4-4-C≡CC 6H 4-4-NO 2)(PPh 3) (11). The optical absorption maximum red-shifts and the first hyperpolarizabilities increase on -system lengthening and on introduction of electron-releasing substituents on the -bridge ring adjacent to the metal centre. The cubic non-linear optical properties of 1,4-{(PCy 3)Au(C≡C)} 2C 6H 4 (12) and {(PCy 3)Au(C≡C-4-C 6H 4C≡C)} 6C 6 (13) have been assessed by wide spectroscopic range femtosecond Z-scan studies; the maximal values of the imaginary component and the effective two-photon absorption cross-section increase markedly on proceeding from linear complex 12 to 6-fold-symmetric complex 13, an increase that is maintained when data are scaled by relative molecular weight.
UR - http://www.scopus.com/inward/record.url?scp=84864912301&partnerID=8YFLogxK
U2 - 10.1071/CH12054
DO - 10.1071/CH12054
M3 - Article
SN - 0004-9425
VL - 65
SP - 834
EP - 841
JO - Australian Journal of Chemistry
JF - Australian Journal of Chemistry
IS - 7
ER -