Enhanced Emission from Single Component Organic Core–Shell Nanoparticles

Abstract

By one-step mixed-solvent mediated approach, we have prepared fluorescent organic core-shell nanoparticles with an oligomer (1) derived from the Schiff base condensation reaction of 2,6-diformyl-4-methylphenol and o-phenylenediamine at room temperature. The core and shell structures are generated by the same oligomer (1) featuring the aggregation structure in core different from that in shell. The radial packing factor distribution of oligomer cluster depending on the solvent interaction in the time of nucleation is mainly responsible for the single component core-shell formation. Different morphologies of the core-shell nanospheres (CSNS) and core-shell nanohemispheres (CSNHS) were generated simply by changing the concentration of 1 in chloroform-methanol mixed solvent (1:2). We observed that fluorescent emission from those core-shell nanoparticles is intense whereas as-synthesized oligomer (1) itself is non-fluorescent in dilute solution. The enhanced emission in the core-shell form with more than 50 times increase in fluorescent quantum yield vis-à-vis 1 is a remarkable feature of the study. As UV absorption spectra of nanoparticles are blue-shifted relative to their properties in solution, the observed strong emission in the solid state makes the oligomer an outstanding exception to a well-established rule based on the molecular exciton model. The core-shell nanoparticles have been characterized by FE-SEM, TEM, XRD, nanosecond (ns) time-resolved fluorescence dynamics, UV-Vis and fluorescence spectroscopy. The longer fluorescence lifetimes (tau) of core-shell nanoparticles (3.50 ns and 3.52 ns for CSNS and CSNHS respectively) than 1 as-synthesized (1.28 ns) implies that the formation of the nanoparticles restricts the rotation and vibration of the groups in the molecules. The factor that induces fluorescent enhancement of nanoparticles is mainly ascribed to the increase of radiative rate constant (k(r)) and simultaneous decrease of nonradiative rate constant (k(nr)).