21021-41-0Relevant articles and documents
ABAB homoleptic bis(phthalocyaninato)lutetium(III) complex: Toward the real octupolar cube and giant quadratic hyperpolarizability
Ayhan, Mehmet Menaf,Singh, Anu,Hirel, Catherine,Guerek, Ayse Guel,Ahsen, Vefa,Jeanneau, Erwann,Ledoux-Rak, Isabelle,Zyss, Joseph,Andraud, Chantal,Bretonniere, Yann
, p. 3655 - 3658 (2012)
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, 〈βHLS2〉1907 = 5750 × 10 -30 esu.
Optimized synthesis and crystal growth by sublimation of 1,3,3-trichloroisoindolenines, key building blocks for crosswise phthalocyanines
Ayhan, Mehmet Menaf,Zorlu, Yunus,Goekdemir, Oezlem,Guerek, Ayse Guel,Dumoulin, Fabienne,Ahsen, Vefa,Hirel, Catherine
, p. 6556 - 6563 (2014)
Among possible asymmetrically substituted phthalocyanines, ABAB derivatives remain rare. Their selective synthesis is based on the use of trichloroisoindolenines, so far remaining tedious to obtain. An optimized synthesis of 1,3,3-trichloroisoindolenine 1 and 1,3,3,6,7- pentachloroisoindolenine 2 is reported. An original crystallization method based on crystal growth by sublimation was eminently suitable regarding the air-sensitivity of these derivatives and allowed their thorough crystallographic characterization. This journal is the Partner Organisations 2014.