Abstract
Zeolite microcrystals can act as host for supramolecular organization of
molecules, complexes, clusters and quantum size particles. They allow
the design of precise and reversible functionalities. Techniques for
arranging zeolite microcrystals of good quality and narrow size
distribution as dense monograin layers on different substrates can be
used to realize specific properties. The chemical reactivity between the
intercalated molecules offer possibilities for in situ synthesis of
molecular chains, clusters and quantum size particles which might not be
accessible otherwise. In some cases guest-host reactivity must be
considered. The reactivity of intercalated compounds with (small)
molecules penetrating from the outside is an option for changing the
composition of a material, i.e. molecules intercalated as monomers in a
first step can be linked to form chains. New electronic structures are
accessible either by specific geometrical arrangements made possible by
the structure of the host and/or by explicitly involving its electronic
properties. Some systems meet the conditions necessary for the
occurrence of intrazeolite charge transport (ionic and electronic),
realized by the guests in their ground state and in electronically
excited states under high vacuum conditions or in the presence of a
solvent, depending on the composition and the structure of the material.
In this article I focus on organic dye molecules in the one-dimensional
channels of zeolites with a hexagonal framework. This system consists of
supramolecularly organized dye molecules. It is shown to provide
fascinating possibilities for building an artificial antenna device
which consists of highly concentrated monomeric dye molecules of up to
0.4 M with a large Förster energy transfer radius and a high
luminescence quantum yield in an ideal geometrical arrangement of
optimal size. Extremely fast electronic excitation energy transport has
been demonstrated by us in oxonine and pyronine dye loaded zeolite L
microcrystals. Many other highly organized dye/zeolite materials can be
prepared and they are expected to show a wide variety of challenging
properties. We report on methods to distinguish between dye molecules
which are inside of a microcrystal and those adsorbed on its outer
surface and we explain a demonstration experiment illustrating the
intercalation of thionine into zeolite L and the thus resulting improved
chemical stability of this dye.
published in: CHIMIA 1998, 52, 525.
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