TY - JOUR
T1 - Iron and Ruthenium Alkynyl Complexes with 2-Fluorenyl Groups
T2 - Some Linear and Nonlinear Optical Absorption Properties
AU - Malvolti, Floriane
AU - Rouxel, Cedric
AU - Grelaud, Guillaume
AU - Toupet, Loic
AU - Roisnel, Thierry
AU - Barlow, Adam
AU - Yang, Xinwei
AU - Wang, Genmiao
AU - Abdul Razak, Fazira I.
AU - Stranger, Robert
AU - Cifuentes, Marie P.
AU - Humphrey, Mark G.
AU - Mongin, Olivier
AU - Blanchard-Desce, Mireille
AU - Paul-Roth, Christine O.
AU - Paul, Frédéric
N1 - Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/8
Y1 - 2016/8
N2 - Four new mononuclear alkynyl complexes each featuring a terminal 2-fluorenyl group, namely Fe(η5-C5Me5)(CO)2[C≡C(2-C21H25)] (2), Ru(κ2-dppe)2Cl[C≡C(2-C21H25)] (3), Ru(κ2-dppe)2[C≡C(4-C6H4NO2)][C≡C(2-C21H25)] (4), and [Fe(η5-C5Me5)(κ2-dppe){C≡C(C5H4N)-CH2(2-C13H9)}][PF6] (5[PF6]), have been synthesized and characterized, and their redox, absorption, and emission properties have been studied. For the two ruthenium derivatives 3 and 4, these studies are complemented by spectroelectrochemical investigations, Z-scan measurements, and DFT calculations. Fluorimetric studies reveal that these compounds are poorly or not luminescent, and, when luminescent, that the detected weak luminescence most likely originates from a higher lying ligand-centred (LC) excited state presumably located on fluorene. Finally, the third-order nonlinear optical (NLO) properties of 3 and 4 are reported. It is shown that the bis-alkynyl complex 4 is significantly more active than 3 and that both compounds exhibit two-photon absorption (TPA) around 860–1050 nm, with TPA cross-sections above 350 GM. In addition, it is shown that both species should give rise to a marked switching of their cubic NLO properties in this spectral range upon oxidation.
AB - Four new mononuclear alkynyl complexes each featuring a terminal 2-fluorenyl group, namely Fe(η5-C5Me5)(CO)2[C≡C(2-C21H25)] (2), Ru(κ2-dppe)2Cl[C≡C(2-C21H25)] (3), Ru(κ2-dppe)2[C≡C(4-C6H4NO2)][C≡C(2-C21H25)] (4), and [Fe(η5-C5Me5)(κ2-dppe){C≡C(C5H4N)-CH2(2-C13H9)}][PF6] (5[PF6]), have been synthesized and characterized, and their redox, absorption, and emission properties have been studied. For the two ruthenium derivatives 3 and 4, these studies are complemented by spectroelectrochemical investigations, Z-scan measurements, and DFT calculations. Fluorimetric studies reveal that these compounds are poorly or not luminescent, and, when luminescent, that the detected weak luminescence most likely originates from a higher lying ligand-centred (LC) excited state presumably located on fluorene. Finally, the third-order nonlinear optical (NLO) properties of 3 and 4 are reported. It is shown that the bis-alkynyl complex 4 is significantly more active than 3 and that both compounds exhibit two-photon absorption (TPA) around 860–1050 nm, with TPA cross-sections above 350 GM. In addition, it is shown that both species should give rise to a marked switching of their cubic NLO properties in this spectral range upon oxidation.
KW - Alkynyl complexes
KW - Electrochemistry
KW - Luminescence
KW - Nonlinear optics
KW - Redox chemistry
KW - Two-photon absorption
UR - https://www.scopus.com/pages/publications/84980000194
U2 - 10.1002/ejic.201600598
DO - 10.1002/ejic.201600598
M3 - Article
SN - 1434-1948
VL - 2016
SP - 3868
EP - 3882
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 24
ER -