In situ synthesis of fluorescent poly(norbornene)/oxazine-1 dye loaded fluoromica hybrids: supramolecular control over dye arrangement

We report on the in situ synthesis of fluorescent poly(norbornene)/oxazine-1 (Ox1) dye loaded fluoromica mineral Somasif (SME) hybrid materials. SME acts as host for supramolecular arrangement of Ox1 molecules in their 2D interlayer region. The dye arrangement is easily tuned by modulating the dye loading as well as by competitive intercalation with an ammonium surfactant. The dye molecules bend at most by 30 degrees with respect to the SME layer surface increasing the dye loading up to 69% of the clay cation exchange capacity (CEC). This Ox1 state provides accessible interlayer voids which in turn facilitate the entry of polymerizable monomers (i.e., norbornene and ethylene) and the in situ growth of the polymer. In this way a highly processable polymer hybrid, in which the dye molecules are highly oriented in the inorganic framework, is formed. The optical spectroscopy shows unique J-band characteristics along with the Ox1 monomer features. The formation of the J-aggregates is likely induced by the interlayer segregated poorly polar norbornene phase that forces the Ox1 molecules to increase the head-to-tail interaction between them. These features strongly encourage the technical application of these materials for fabricating functional devices with unique photoluminescence properties.