TY - JOUR
T1 - Nonlinear Optical Properties of Fe(II) and Ru(II) Alkynyl-Functionalized 1,3,5-Triphenyl-1,3,5-triazine-2,4,6-triones and 1,3,5-Triphenylbenzenes
T2 - Syntheses, Second-Harmonic Generation and Two-Photon Absorption
AU - Trujillo, Alexander
AU - Veillard, Romain
AU - Triadon, Amédée
AU - Grelaud, Guillaume
AU - Argouarch, Gilles
AU - Roisnel, Thierry
AU - Singh, Anu
AU - Ledoux, Isabelle
AU - Amar, Anissa
AU - Boucekkine, Abdou
AU - Samoc, Marek
AU - Matczyszyn, Katarzyna
AU - Yang, Xinwei
AU - Barlow, Adam
AU - Cifuentes, Marie P.
AU - Morshedi, Mahbod
AU - Humphrey, Mark G.
AU - Paul, Frédéric
N1 - Publisher Copyright:
© 2026 by the authors.
PY - 2026/3
Y1 - 2026/3
N2 - We report the use of σ-alkynyl d6 electron-rich transition metal complexes as electron-releasing end-groups in octupolar molecules designed for nonlinear optical (NLO) applications, specifically, N,N′,N″-triarylisocyanurates (5,7,8,10,12) and 1,3,5-triarylbenzenes (6,9,11) functionalized by Fe(II) and Ru(II) organometallic moieties, and their NLO properties, as assessed by hyper-Rayleigh scattering (HRS) and Z-scan. The redox properties are briefly investigated through isolation of the corresponding Fe(III) trications 5[PF6]3 and 6[PF6]3. The second-harmonic generation (SHG) or two-photon absorption (2PA) performance of the Fe(II) and Ru(II) parents is compared with the help of TD-DFT calculations performed on models. Comparison with tris-ferrocenyl isocyanurate 4 reveals that the σ-connection of the metallic centers to the π-manifold is superior to the η5-connection for enhancing NLO properties. The positive effect of organometallic end-groups on NLO properties relative to purely organic electron-releasing substituents is established. The mechanism by which NLO enhancement occurs is complex and possibly connected to the polarizable π-electrons in the ligands surrounding the metal alkynyl units, but in most cases, the observed NLO enhancement must arise from the transition metal centers interacting with the central π-manifold.
AB - We report the use of σ-alkynyl d6 electron-rich transition metal complexes as electron-releasing end-groups in octupolar molecules designed for nonlinear optical (NLO) applications, specifically, N,N′,N″-triarylisocyanurates (5,7,8,10,12) and 1,3,5-triarylbenzenes (6,9,11) functionalized by Fe(II) and Ru(II) organometallic moieties, and their NLO properties, as assessed by hyper-Rayleigh scattering (HRS) and Z-scan. The redox properties are briefly investigated through isolation of the corresponding Fe(III) trications 5[PF6]3 and 6[PF6]3. The second-harmonic generation (SHG) or two-photon absorption (2PA) performance of the Fe(II) and Ru(II) parents is compared with the help of TD-DFT calculations performed on models. Comparison with tris-ferrocenyl isocyanurate 4 reveals that the σ-connection of the metallic centers to the π-manifold is superior to the η5-connection for enhancing NLO properties. The positive effect of organometallic end-groups on NLO properties relative to purely organic electron-releasing substituents is established. The mechanism by which NLO enhancement occurs is complex and possibly connected to the polarizable π-electrons in the ligands surrounding the metal alkynyl units, but in most cases, the observed NLO enhancement must arise from the transition metal centers interacting with the central π-manifold.
KW - 2,4,6-triphenylbenzenes
KW - DFT calculations
KW - metal alkynyl complexes
KW - nonlinear optics
KW - octupoles
KW - triarylisocyanurates
UR - https://www.scopus.com/pages/publications/105034328648
U2 - 10.3390/photochem6010006
DO - 10.3390/photochem6010006
M3 - Article
AN - SCOPUS:105034328648
SN - 2673-7256
VL - 6
JO - Photochem
JF - Photochem
IS - 1
M1 - 6
ER -