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Electronic and Vibrational Properties of Fluorenone in the Channels of Zeolite L
Author(s) -
Devaux André,
Minkowski Claudia,
Calzaferri Gion
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305673
Subject(s) - fluorenone , zeolite , luminescence , raman spectroscopy , chemistry , absorption (acoustics) , homo/lumo , fourier transform infrared spectroscopy , absorption band , analytical chemistry (journal) , absorption spectroscopy , molecule , photochemistry , materials science , optics , optoelectronics , organic chemistry , fluorene , composite material , catalysis , polymer , physics
Fluorenone (C 13 H 8 O) was inserted into the channels of zeolite L by using gas‐phase adsorption. The size, structure, and stability of fluorenone are well suited for studying host–guest interactions. The Fourier transform IR, Raman, luminescence, and excitation spectra, in addition to thermal analysis data, of fluorenone in solution and fluorenone/zeolite L are reported. Normal coordinate analysis of fluorenone was performed, based on which IR and Raman bands were assigned, and an experimental force field was determined. The vibrational spectra can be used for nondestructive quantitative analysis by comparing a characteristic dye band with a zeolite band that has been chosen as the internal standard. Molecular orbital calculations were performed to gain a better understanding of the electronic structure of the system and to support the interpretation of the electronic absorption and luminescence spectra. Fluorenone shows unusual luminescence behavior in that it emits from two states. The relative intensity of these two bands depends strongly on the environment and changes unexpectedly in response to temperature. In fluorenone/zeolite L, the intensity of the 300 nm band (lifetime 9 μs) increases with decreasing temperature, while the opposite is true for the 400 nm band (lifetime 115 μs). A model of the host–guest interaction is derived from the experimental results and calculations: the dye molecule sits close to the channel walls with the carbonyl group pointing to an Al 3+ site of the zeolite framework. A secondary interaction was observed between the fluorenone's aromatic ring and the zeolite's charge‐compensating cations.