Barun Dhara

Increase in Electrical Conductivity of MOF to Billion-Fold upon Filling the Nanochannels with Conducting Polymer

Redox-active pyrrole (Py) monomers were intercalated into 1D nanochannels of [Cd(NDC)0.5(PCA)]·Gx (H2NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) (1) - a fluorescent 3D MOF (λem = 385 nm). Subsequent activation of 1⊃Py upon immersing into iodine (I2) solution resulted in an increment of the bulk electrical conductivity by ∼9 orders of magnitude. The unusual increase in conductivity was attributed to the formation of highly oriented and conducting polypyrrole (PPy) chains inside 1D nanochannels and specific host-guest interaction in 1⊃PPy thereof. The Hall-effect measurements suggested 1⊃PPy to be an n-type semiconductor material with remarkably high-carrier density (η) of ∼1.5 × 10(17) cm(-3) and mobility (μ) of ∼8.15 cm(2) V(-1) s(-1). The fluorescence property of 1 was almost retained in 1⊃PPy with concomitant exciplex-type emission at higher wavelength (λem = 520 nm). The here-presented results on [MOF⊃Conducting Polymer] systems in general will serve as a prototype experiment toward rational design for the development of highly conductive yet fluorescent MOF-based materials for various optoelectronic applications.

In situ generation of conducting polymer in a redox-active metal–organic gel

Metal–organic gels (MOGs) are evolving as a new class of stimuli-responsive materials. A redox-active MOG comprised of a ferric ion and benzene tricarboxylic acid ligand was prepared and characterized. In situ incorporation (without the use of any extraneous oxidant) of conducting polypyrrole and polythiophene moieties into the xerogel matrix was achieved, and thereby resulted in the formation of hybrid composite materials.

Selective Sensing of Metal Ions and Nitro Explosives by Efficient Switching of Excimer-to-Monomer Emission of an Amphiphilic Pyrene Derivative

An amphiphilic pyrene derivative exhibiting unusually stable excimer emission due to strong aggregation is presented. The aggregated system served as an intelligent sensor for metal ions and nitro explosives in aqueous media. The excimer displayed excellent selectivity toward Cu2+ among the tested cations. The observation was interpreted on the basis of chelation of metal ions involving the hydroxyl and amino groups of two molecules, leading to the ligand-to-metal charge-transfer (CT) process. The excimer was further applied for the cell imaging of Cu2+ ions. Also, while treating the excimer with various nitro explosives, it displayed efficient 2,4,6-trinitrophenol sensing, corroborating mainly the CT process from pyrene to the analyte due to intercalation of the analyte within pyrene.