Formation of Novel Layered Nanostructures from Lanthanide-Complexes by Secondary Interactions with Ligating Monomers in Miniemulsion Droplets

The addition of neutral, inert inner shell lanthanide complexes such as Gd(III)‐(tmhd)3, Eu(III)‐(fod)3, or Ho(III)‐thmd3, broadly available as NMR shift reagents, towards ester‐containing monomers such as butyl acrylate and subsequent polymerization in miniemulsion droplets leads to the spontaneous formation of highly organized layered nanocomposite particles, as revealed by electron microscopy and small angle X‐ray scattering. The nanocomposite comprises a lanthanide complex phase and a polymer phase with a lamellar repeat period of about 3.5 nm, rather independent of the system composition. TEM micrograph of a PGd‐3 nanocomposite and corresponding chemical structure of the complex Gd(tmhd)3.