Synthesis and applications of some upper and lower rim functionalized calix[4]arenes and calix[4]naphthalene derivatives

Valluru, Gopikishore (2015) Synthesis and applications of some upper and lower rim functionalized calix[4]arenes and calix[4]naphthalene derivatives. Doctoral (PhD) thesis, Memorial University of Newfoundland.

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Abstract

The work described in this thesis is concerned mainly with the synthesis and characterization of bimodal calix[4]arene and calix[4]naphthalene derivatives. Their complexation properties with some Group 1, Group 2 and transition metal cation guests were studied. Chapter 1 provides an overview of supramolecular chemistry, calixarenes and calixnaphthalenes and the methods employed herein. In Chapter 2, the synthesis of some selected upper- and lower-rim functionalized calix[4]arene derivatives and their complexation studies are described. The lower rim of the calix[4]arene derivatives are modified with O-methyl, O-ethyl esters and crown ether moieties which selectively bind to Group 1 and 2 metal ions. Current studies on the development of a microcantilever (MCL)-based real-time device employing modified calix[4]arene-derived sensing layers are on-going in collaborative work with Dr. L.Y. Beaulieu‘s group in the Department of Physics and Physical Oceanography at Memorial University. In order to test the selectivity for different metal ions with the sensing layers needed for the different MCLs envisioned in the MCL instrument; the work described in Chapter 3 concerns the synthesis and applications of new triazole-bridged anthracene/pyrene-appended calix[4]arene derivatives. The synthetic strategy involved a ―click‖ reaction as the key step. In the study reported herein, their complexation properties with various metal ions were investigated by fluorescence, UV-vis and 1H-NMR spectroscopic analyses. Chapter 4, describes the synthesis and applications towards selective metal ion recognition by a calix[4]arene-NHC (N-heterocyclic carbene) derivative. The lower rim of the calix[4]arene was functionalized with two different groups, one of which consists of a 1,3 bridged ―crown-5‖ and the other 1,3 positions with imidazole groups. The resulting NHC enables the calix[4]arene to potentially form a stable self-assembled monolayer (SAM) on the Au surface of a microcantilever. In Chapter 5, the synthesis of some sulfonated calix[4]naphthalene derivatives and their complexation studies are described. In another collaborative project with Prof. A. Coleman‘s group at the University of Lyon, these naphthalene derivatives were shown to be capable of capping and stabilizing silver nanoparticles. Along with these properties, cyclotetrachromotropylene (―CTCT‖) was characterized and shown to be capable of selectively dispersing SWNTs into water. The resulting supramolecular complexes in a collaborative project with Y. Zhao‘s group at Memorial University and A. Adronov‘s group at McMaster University were characterized by Atomic Force Microscopy (AFM), Raman spectroscopy and UV-Vis-NIR analysis.

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