Styryl dyes are generally poor fluorescent molecules inherited from their flexible molecular structures. However, their emissive properties can be boosted by restricting their molecular motions. A tight confinement into inorganic molecular sieves is a good strategy to yield highly fluorescent hybrid systems. In this work, we compare the confinement effect of two Mg-aluminophosphate zeotypes with distinct pore systems (the AEL framework, a one-dimensional channeled structure with elliptical pores of 6.5 Å × 4.0 Å, and the CHA framework, composed of large cavities of 6.7 Å × 10.0 Å connected by eight-ring narrower windows) for the encapsulation of 4-DASPI styryl dye (trans-4-[4-(Dimethylamino)styryl]-1-methylpyridinium iodide). The resultant hybrid systems display significantly improved photophysical features compared to 4-DASPI in solution as a result of tight confinement in both host inorganic frameworks. Molecular simulations reveal a tighter confinement of 4-DASPI in the elliptical channels of AEL, explaining its excellent photophysical properties. On the other hand, a singular arrangement of 4-DASPI dye is found when confined within the cavity-based CHA framework, where the 4-DASPI molecule spans along two adjacent cavities, with each aromatic ring sitting on these adjacent cavities and the polymethine chain residing within the narrower eight-ring window. However, despite the singularity of this host-guest arrangement, it provides less tight confinement for 4-DASPI than AEL, resulting in a slightly lower quantum yield.
Keywords: AEL framework; CHA framework; MgAPO; aluminophosphates; cavities; fluorescence; molecular sieves; nanochannels; photoactive hybrid systems; styryl dyes.