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Covalent Functionalization of Organic Nanoparticles Using Aryl Diazonium Chemistry and Their Solvent-Dependent Self-Assembly

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journal contribution
posted on 06.01.2017, 00:00 by Sreedevi Krishnakumar, Karical R. Gopidas
A simple method for covalent functionalization of Fréchet-type dendron nanoparticles (FDNs) using tris-bipyridylruthenium­(II) is described. Covalent functionalization is achieved by chemically reducing the diazo derivative of a ruthenium­(II)­bipyridine complex in the presence of FDNs wherein the radical species generated gets covalently linked to the nanoparticle surface. Simplicity, rapidity, and robustness are the advantages offered by the present approach. The nanoparticles, post functionalization, were characterized using transmission electron microscopy, thermogravimetric analysis, and infrared, energy-dispersive X-ray, UV–visible, and nuclear magnetic resonance spectroscopic techniques. Depending on the solvent, the ruthenium complex-linked FDN displays a range of morphologies, including nanoparticles, fiber-networks, and nanocapsules. In the nanocapsules and fiber-networks observed in organic solvents, the ruthenium complex is confined within the interior domain of the aggregate, whereas in the nanoparticles observed in water, it is present on the periphery. The formation of predictable morphologies in different solvents plays a key role in using such self-assembled structures for various applications such as sensing, catalysis, and light harvesting. Characterization of these nanoaggregates using different spectroscopic and microscopic techniques is also described.