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.
ABAB homoleptic bis(phthalocyaninato)lanthanide(III) complexes: Original octupolar design leading to giant quadratic hyperpolarizability
Ayhan, Mehmet Menaf,Singh, Anu,Jeanneau, Erwann,Ahsen, Vefa,Zyss, Joseph,Ledoux-Rak, Isabelle,Guerek, Ayse Guel,Hirel, Catherine,Bretonniere, Yann,Andraud, Chantal
, p. 4359 - 4370 (2014)
The octupolar cube, a Td symmetry cube presenting alternating charges at its corners, is the generic point charge template of any octupolar molecule. So far, transposition into real molecular structures has yet to be achieved. We report here a first step toward the elaboration of fully cubic octupolar architectures. A series of octupolar bis(2,3,16,17-tetra(hexylthio) phthalocyaninato)lanthanide double-decker complexes [Pc2Ln], Ln = Nd (1), Eu (2), Dy (3), Y (4), and Lu (5), are described, whose original three-dimensional structures display the required alternation of ABAB type for one face of the cube and the delocalization between the two rings approximating to the electronic interaction along the edges of the cube. Synthesis, X-ray crystal structure, and study of the optical properties and of the first molecular hyperpolarizability β are reported. The size of the lanthanide (III) central ion modulates the ring-to-ring distance and the degree of coupling between the two phthalocyanine rings. As a consequence, the optical properties of these octupolar chromophores and in particular the strong near-infrared absorption due to the intervalence transition between the two rings also depend on the central lanthanide (III) ion. The first oxidized and reduced states of the complexes, while keeping a similar octupolar structure, display considerably changed optical properties compared to the neutral states. Second-order nonlinear properties were determined by nonpolarized harmonic light scattering in solution at 1907 nm. Exceptionally large dynamic molecular first hyperpolarizabilities √ βHLS21907, among the highest ever reported, were found that showed a strong dependence on the number of 4f electrons.
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.
The structures of several modified isoindolines, the building blocks of phthalocyanines
Engle, James T.,Allison, Ashley N.,Standard, Joshua M.,Tamgho, Ingrid-Suzy,Ziegler, Christopher J.
, p. 712 - 721 (2013/09/24)
This report presents the single crystal X-ray structures of several substituted isoindolines that have been frequently used as starting materials for phthalocyanines, phthalocyanine analogs and related chelates. The structures of 1,3-diiminoisoindoline (1), 1,3-bis(hydroxyimino)isoindoline (2), 1,4-diaminophthalazine (3), 1,1,3-trichloroisoindoline (4) and 3-imino-1-oxoisoindoline (5) are reported; compounds 2 and 3 are synthesized from diiminoisoindoline (1) and 4 and 5 are produced from phthalimide. All five compounds are planar macrocycles, and localization of double bonds can be readily determined. We elucidated one of the known structures of 1 at low temperature, and observed two additional new structures of 1. For the crystal forms of 1 and compounds 2, 3, and 5, hydrogen bonding in the solid state was observed. Compounds 1, 2 and 3 form extended hydrogen bonded arrays in the solid state, whereas 5 forms discrete hydrogen bonded dimers.
