Since 1987, high-luminance low-voltage driven devices based on tris(8-hydroxyquinoline)aluminum(III) (Alq 3 ) opened the route to design low-cost large area displays and illuminators. Despite the large number of studies devoted to this material, very little is known about its basic structural and optical properties in the solid state. Therefore, we have investigated the structure(s) and the correlation between intermolecular interactions and optical properties in various Alq 3 systems, including solution, amorphous thin films, and different crystalline forms. Two novel unsolvated polymorphs of Alq 3 , namely, R-Alq 3 and -Alq 3 , have been synthesized and their crystalline structures determined from X-ray diffraction data on powders (R) and single crystals ( ). Crystals of R-Alq 3 are triclinic, space group P-1, a ) 6.2586 (8) Å, b ) 12.914(2) Å; c ) 14.743(2) Å, R ) 109.66(1)°; ) 89.66(1)°, and γ ) 97.68(1)°; crystals of -Alq 3 are triclinic, space group P-1, a ) 8.4433(6) Å, b ) 10.2522(8) Å; c ) 13.1711(10) Å, R ) 108.578(1)°, ) 97.064(1)°, and γ ) 89.743 (1)°. Both these crystal structures consist of a racemic mixture of the mer isomer, but are characterized by different molecular packings involving well-defined short contacts between quinoxaline ligands belonging to symmetry-related Alq 3 molecules with interligand spacings in the 3.5-3.9 Å range. A third "high-temperature" phase, γ-Alq 3 , was found to contain orientationally disordered mer-Alq 3 molecules, lying about a 32 position of the trigonal P-31c space group, with a ) 14.41(1) Å and c ) 6.22(1) Å. In addition, a hemichlorobenzene adduct of Alq 3 was also prepared and structurally characterized (monoclinic, space group P2 1 /n, a ) 10.786(1) Å, b ) 13.808(2) Å, c ) 16.928(2) Å, ) 97.90(2)°). Investigations of the different crystal phases, as well as of amorphous thin films and solutions by absorption, fluorescence excitation, fluorescence, and Raman spectroscopy, allowed the effect of the molecular packing on the emission properties to be elucidated, the nature of the photoexcitations to be clarified, and the vibrational fingerprints of the R and crystalline forms to be highlighted. The spectral position of fluorescence is found to be correlated with both the molecular density of the packing and the length of interligand contacts between neigboring Alq 3 molecules as a consequence of different dispersive and dipolar interactions as well as different π-π orbital overlaps (the shorter the contacts, i.e., the denser the crystal, the more the fluorescence is red-shifted). The low-temperature (4.2 K) vibronic structure of the fluorescence spectrum of Alq 3 is resolved for the first time. It is assigned to the FranckCondon activity of an in-plane bending mode at ca. 525 cm -1 , and it is symptomatic of the ligand-centered nature of the optical transitions. From the analysis of the vibronic progression the existence of a strong electronphonon coupling involving the 525 cm -1 mode with a Huang-Rhys factor of ca. 2.6 ( 0.4 is inferred. The origin of the amorp...

Abstact:The aim of this paper is to present an overview of the recent achievements of our group in the fabrication and optical characterizations of As 2 S 3 microstructured optical fibers (MOFs). Firstly, we study the synthesis of high purity arsenic sulfide glasses. Then we describe the use of a versatile process using mechanical drilling for the preparation of preforms and then the drawing of MOFs including suspended core fibers. Low losses MOFs are obtained by this way, with background level of losses reaching less than 0.5 dB/m. Optical characterizations of these fibers are then reported, especially dispersion measurements. The feasibility of all-optical regeneration based on a Mamyshev regenerator is investigated, and the generation of a broadband spectrum between 1 µm and 2.6 µm by femto second pumping around 1.5 µm is presented.

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