A simple and efficient protocol is developed for the in situ generation of highly monodisperse and small (2−3 nm) silver nanoparticles in poly(vinyl alcohol) film and the fabrication of their free-standing films. Efficient optical limiting with these nanoparticle-embedded polymer thin films is demonstrated.

Metal nanoparticle-polymer composites are versatile materials which not only combine the unique characteristics of the components, but also manifest mutualistic effects between the two. Embedding inside polymer thin films facilitates immobilization and organization of the metal nanoparticles and tuning of their electronic and optical responses by the dielectric environment. The embedded metal nanoparticles in turn can impact upon the various material attributes of the polymer matrix. Some of the most convenient and attractive routes to the fabrication of metal nanoparticle-embedded polymer thin films involve in situ generation of the nanoparticles through reduction or decomposition of appropriate precursors inside the solid film. In this tutorial review we present an overview of the different methodologies developed using this general concept and describe the environment-friendly protocol we have optimized for the fabrication of noble metal nanostructures inside polymer thin films, using aqueous media for the synthesis and deploying the polymer itself as the reducing as well as stabilizing agent. A variety of techniques that have been exploited to characterize the precursor to product transformation inside the polymer film are discussed. The unique control provided by the in situ fabrication route on the size, shape and distribution of the nanostructures, and application of the polymer thin films with the in situ generated metal nanoparticles in areas such as nonlinear optics, surface enhanced Raman scattering, e-beam lithography, microwave absorption, non-volatile memory devices and random lasers, illustrate the versatility of these materials. A brief appraisal of the avenues for future developments in this area is presented.

Intermolecular interactions, such as hydrogen bonding, dipolar and van der Waals, occurring in molecular crystals cover a range of magnitudes. As the crystal evolves from a relatively softer state in the nanoscopic size regime to a harder one in the microcrystalline and bulk solid state, the impact of the hierarchy of intermolecular interactions can be expected to emerge in a progressive fashion. The strongest interactions alone would be manifested at small sizes; as the crystal grows, the effect of the weaker ones will be added on, with the bulk crystals exhibiting the cumulative impact of the different interactions. We demonstrate this phenomenon through investigations of the solution, colloid, and solid state of a novel zwitterionic molecule based on the diaminodicyanoquinodimethane framework. A reprecipitation-digestion protocol is developed for the fabrication of nano/microcrystals of varying sizes. Microscopic and spectroscopic characterizations reveal tuning of the size and optical properties of this material. The optical absorption of the colloidal particles evolves with size towards that of the bulk solid, the emission showing a steady enhancement of intensity. Crystallographic investigations coupled with semiempirical computations provide a viable model to describe the range of observations in terms of the gradual accumulation of hierarchical intermolecular interactions.

Remote functionalized zwitterionic diaminodicyanoquinodimethanes are found to exhibit a dramatic enhancement of light emission in the solid state and when doped in polymer films, as compared to the solution state. Crystal structure analysis of prototypical molecules reveals the role of the remote functionality in the solid state molecular organization. Semiempirical quantum chemical computations provide a viable model to explain the interesting phenomenon of fluorescence enhancement as arising from the inhibition of geometry relaxation of the vertical excited state to a nonemitting state. The reversible switching of a doped polymer film fluorescence triggered by solvent vapors is demonstrated.