ABAB Homoleptic Bis(phthalocyaninato)lutetium(III) Complex: Toward the Real Octupolar Cube and Giant Quadratic Hyperpolarizability

Abstract

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.

Mechanism of the Zn(II)Phthalocyanines’ Photochemical Reactions Depending on the Number of Substituents and Geometry

“…Residual water in zinc acetate salts Zn(OAc) 2 was removed by heating at 120˝C under vacuum (10´2 mm Hg). 2,3,16,17-tetra(hexylthio)phthalocyanine (ABAB-H2) and 2,3,9,10,16,17 hexakis(hexylthio)phthalocyanine (AB3-H2) were prepared as previously described in [38], as well as (2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyaninato)Zinc (B4) in [39].…”

Pyridone substituted phthalocyanines: Photophysico-chemical properties and TD-DFT calculations

“…Because of their unique spectroscopic and electrochemical properties, metallophthalocyanines (MPc) have found applications as semiconductors, nonlinear optical and optical limiting materials, chemo sensors, organic photovoltaics, catalysis and photo sensitizers for photodynamic therapy and photodynamic inactivation [1][2][3][4][5][6][7][8][9][10][11][12][13]. Pyridone derivatives are hetero cyclic intermediates used for the synthesis of arylazo dyes.…”

Synthesis and electrochemistry of phthalocyanines bearing [(3,4-dimethoxybenzyl)oxy] groups

“…Therefore, this class of compounds exhibits technological applications in different areas such as chemical sensors, 1−3 solar cells, 4−6 gas sensors, 7−9 liquid crystals, 10,11 optical data storage, 12,13 photodynamic therapy, 14−18 nonlinear optics, 19 and electrochemical applications such as electroctalytic, 20,21 electrosensing, 22,23 and electrochromic materials.…”