TY - JOUR
T1 - Two-photon absorption properties of iron(II) and ruthenium(II) trischelate complexes of 2,2′:4,4″:4′,4‴-quaterpyridinium ligands
AU - Coe, Benjamin J.
AU - Samoc, Marek
AU - Samoc, Anna
AU - Zhu, Lingyun
AU - Yi, Yuanping
AU - Shuai, Zhigang
PY - 2007/1/25
Y1 - 2007/1/25
N2 - A series of RuII or FeII trischelate complex salts containing N-methyl/aryl-2,2′:4,4″:4′,4‴- quaterpyridinium ligands that has previously been subjected to quadratic nonlinear optical studies (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 13399) has now been investigated for two-photon absorbing behavior. Z-scan measurements using a 750 nm laser afford reasonably large two-photon absorption (2PA) cross-sections σ2 of ca. 62-180 GM for the Ru II complexes, but only very weak 2PA is observed for the Fe II compounds. The excited-state and 2PA properties of the representative chromophore [RuII(Me2Qpy2+) 3]8+ (Me2Qpy2+ = N″,N‴-dimethy]-2,2′:4,4″:4′,4‴- quaterpyridinium) have also been investigated by using semiempirical intermediate neglect of differential overlap/multireference-determinant single and double configuration interaction computations with the optimized geometry obtained via density functional theory. The calculated σ2 value of ca. 624 GM at 1.70 eV for this metal-to-ligand charge-transfer chromophore is about 10 times larger than that obtained from the Z-scan studies.
AB - A series of RuII or FeII trischelate complex salts containing N-methyl/aryl-2,2′:4,4″:4′,4‴- quaterpyridinium ligands that has previously been subjected to quadratic nonlinear optical studies (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 13399) has now been investigated for two-photon absorbing behavior. Z-scan measurements using a 750 nm laser afford reasonably large two-photon absorption (2PA) cross-sections σ2 of ca. 62-180 GM for the Ru II complexes, but only very weak 2PA is observed for the Fe II compounds. The excited-state and 2PA properties of the representative chromophore [RuII(Me2Qpy2+) 3]8+ (Me2Qpy2+ = N″,N‴-dimethy]-2,2′:4,4″:4′,4‴- quaterpyridinium) have also been investigated by using semiempirical intermediate neglect of differential overlap/multireference-determinant single and double configuration interaction computations with the optimized geometry obtained via density functional theory. The calculated σ2 value of ca. 624 GM at 1.70 eV for this metal-to-ligand charge-transfer chromophore is about 10 times larger than that obtained from the Z-scan studies.
UR - http://www.scopus.com/inward/record.url?scp=33847000940&partnerID=8YFLogxK
U2 - 10.1021/jp0656072
DO - 10.1021/jp0656072
M3 - Article
SN - 1089-5639
VL - 111
SP - 472
EP - 478
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 3
ER -