ABAB homoleptic bis(phthalocyaninato)lutetium(III) complex: toward the real octupolar cube and giant quadratic hyperpolarizability.
The concept of octupolar molecules has considerably enlarged the engineering of second-order nonlinear optical materials by giving access to 2D and 3D architectures. However, if the archetype of octupolar symmetry is a cube with alternating donor and acceptor groups at the corners, no translation of this ideal structure into a real molecule has been realized to date. This may be achieved by designing a bis(phthalocyaninato)lutetium(III) double-decker complex with a crosswise ABAB phthalocyanine bearing alternating electron-donor and electron-acceptor groups. In this communication, we present the first step toward this goal with the synthesis, crystal structure determination, and measurement of the molecular first-order hyperpolarizability β by harmonic light diffusion, of an original lutetium(III) sandwich complex displaying the required ABAB-type alternation for one face of the cube. This structure is characterized by an intense absorption in the near-IR due to an intervalence transition and exhibits the highest quadratic hyperpolarizability ever reported for an octupolar molecule, √<β(2)(HLS)> = 5750 × 10(-30) esu.
Laboratoire de Chimie de l'ENS de Lyon, CNRS UMR 5182, Université Lyon I, ENS de Lyon, 46 allée d'Italie, 69364 Lyon cedex 07, France.
Mehmet Menaf
MM
Ayhan
Anu
A
Singh
Catherine
C
Hirel
Ayşe Gül
AG
Gürek
Vefa
V
Ahsen
Erwann
E
Jeanneau
Isabelle
I
Ledoux-Rak
Joseph
J
Zyss
Chantal
C
Andraud
Yann
Y
Bretonnière
D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D009942:Organometallic Compounds; C572922:bis(phthalocyaninato)lutetium(III)