Close-packed dye molecules in zeolite channels self-assemble into supramolecular nanoladders

A tough challenge in nanomaterials chemistry is the determination of the structure of multicomponent nanosystems. Dye-zeolite L composites are building blocks of hierarchically organized multifunctional materials for technological applications. Supramolecular organization inside zeolite L nanochannels, which governs electronic properties, is barely understood. This is especially true for confined close-packed dye molecules, a regime not investigated in applications yet and that might have great potential for future development in this field. Here we realize for the first time composites of zeolite L with maximally packed fluorenone molecules and elucidate their structure by integrated multitechnique analyses. By IR spectroscopy, thermogravimetric analysis, and X-ray diffraction, we establish the maximum degree of dye loading obtained (1.5 molecules per unit cell), and by modeling we reveal that at these conditions fluorenone molecules form quasi 1-D supramolecular nanoladders running along the zeolite channels. Spatial and morphological control provided by the nanoporous matrix combined with a complex blend of strong dye-zeolite and weaker dye-dye van der Waals interactions lie at the origin of this unique architecture, which is also stabilized by the hydrogen bond network of coadsorbed water molecules surrounding the dye nanoladder and penetrating between its rungs.