Self-assembly of reactive intermediates at the interface of an immiscible liquid mixture is an emerging bottom-up approach in constructing 2D functional materials. Herein, a mechanistic investigation of the vital role of various oxidants in the self-assembly of reactive intermediates at the water/chloroform interface in pyrrole polymerization is reported. The energetics of one-electron transfer between pyrrole and the hydrated metal ions of the oxidant is rationalized successfully using density functional calculations. The electron microscopic and X-ray characterization techniques confirm the relatively uniform distribution of crystalline metal nanoparticles throughout the polymeric matrix. The predominance of the water/chloroform interface in thinning the polymeric sheets to 1.1 nm, by confining the assembly of polypyrrole (PPy) sheets as minimum as three layers, is approximated from atomic force microscopy images. The metal encapsulated PPy sheets are proved to have potential application in the electrochemical sensing of a potent biomarker, dopamine (DA). The electrochemical detection of DA with the limit of detection of 0.24 μm and their printability on a commercially available screen-printed electrode to detect an appreciable current affirm their potential for various electrochemical sensing applications.

Metal nanoclusters of atomic precision have recently emerged as potential candidates for nonlinear optical applications owing to their strong quantum confinement effects. Herein, we report the nonlinear absorptive and refractive properties of platinum-17 (Pt17) metal nanoclusters stabilized by carbon monoxide and triphenyl phosphine ligands. The open aperture z-scan studies in the nanosecond regime reveal a transmittance dip at the focus characteristic of molecule-like behavior and discrete energy levels. The clusters also exhibited a significantly lower optical limiting threshold value and self-defocusing behavior which can be deployed to resist intense optical radiation. We also demonstrate a photonic crystal cavity-assisted enhancement in the absorptive nonlinearity of the synthesized clusters as a result of intense field localization in the defect layer. Our study throws light on the application of these ultrasmall structures in nanophotonic devices.

Herein, we have demonstrated the complexation reaction of silylene and germylene [PhC(NtBu) 2 EN(TMS) 2 ; E = Si (A) and Ge (B)] with several copper(I) salts and further utilized them (1−6) as efficient catalysts in CuAAC reaction. The copper complexes (2 and 4−6) were synthesized from the reaction of [PhC(NtBu) 2 EN(TMS) 2 ] [E = Si (A) or Ge (B)] and CuX (X = Br, I, and SCN). The molecular structures of 2, 4, 5, and 6 were established by single-crystal X-ray diffraction studies. The density functional theory studies indicate that the bimetallic Cu catalyst facilitates the cycloaddition reaction by anchoring the reactants to the close proximity and reducing the energy gap between the frontier orbitals of the dipole and dipolarophile.