title: Squaraines inside Zeolites: Preparation, Stability, and Photophysical Properties.
abstract: A series of four symmetrical squaraines (ditoylyl, di-m-xylyl, dianisyl, and diresorcinyl) incorporated inside zeolites Y, mordenite, and ZSM-5 have been obtained by treating squaric acid and the corresponding arene in the presence of acid zeolites. Acid sites and high reaction temperatures (150 degrees C) were found to be crucial for the success of the preparation procedure. Surprisingly, this method failed for the preparation of the squaraine derived from N,N-dimethylaniline, which is known to be readily formed from squaric acid in homogeneous phase without a catalyst. The solid samples containing squaraines were characterized by diffuse reflectance and Raman spectroscopies and by thermogravimetry-differential scanning calorimetry. Among the hosts, mordenite was found to be the most general and convenient zeolite for the preparation of the squaraines, while in the other solids either the organic content adsorbed was comparatively smaller (ZSM-5) or some squaraines were not very stable (Y zeolite for ditolyl and dixylyl squaraines). The absorption spectra of the samples correspond to the J-aggregation state of the squaraines, except for some ZSM-5 samples, where simultaneous observation of the bands due to both monomers and aggregates occurs. Aggregation also changes with the water content of the samples. Treatment of the zeolite-bound diresorcinyl squaraine with basic aqueous solutions leads to remarkable variations in the diffuse reflectance and Raman spectra. These changes in the Raman spectrum of the diresorcinyl squaraine were found to be reversible by basic or acid washings. Laser flash photolysis using the 355- or 532-nm output of a Nd-YAG laser (<10 ns pulses; </=20 mJ/pulse) allowed the detection of two different types of long-lived intermediates which depended on the zeolite host. On the basis of the similarity of the UV-vis absorption spectra obtained in solution, these transients have been identified as the radical cation (HY) and the triplet excited state (HMor) of the incorporated squaraine.
authors.affiliation: Instituto de Tecnología Química CSIC-UPV, Universidad Politécnica de Valencia, Apartado 22012, 46071 Valencia, Spain, Department of Chemistry, Dalhousie University, Halifax, NS B3H 4J3, Canada, and Departamento de Tecnología de Industrias Químicas, INETI, IBQTA, Az. dos Lameiros à estrada do Paço do Lumiar, 1699 Lisboa Codex, Portugal.
authors.forename: María Luz
authors.initials: ML
authors.lastname: Cano
authors.forename: Frances L.
authors.initials: FL
authors.lastname: Cozens
authors.forename: María A.
authors.initials: MA
authors.lastname: Esteves
authors.forename: Francisco
authors.initials: F
authors.lastname: Márquez
authors.forename: Hermenegildo
authors.initials: H
authors.lastname: García