Synthesis and Characterization of Luminescent Lanthanide Nano-Rings

It is not uncommon for inorganic chemistry classes to gloss over the chemistry of the lanthanides. Because most inorganic chemists work closely with the d -electrons of the transition metals, the shielded and inert f -electrons of the lanthanides may at first glance seem monotone or even boring. However, to truly appreciate the lanthanides and the complexes they produce, one must come to embrace their chemical simplicity and understand their much more interesting electronic properties that lead to extremely interesting luminescent and magnetic molecules. Furthermore, though the lanthanides generally only form 3+ ions, it is important to consider that their high coordination number can lead to some very large and unusual molecular structures.

Additionally, lanthanide complexes are known for their photophysical properties, specifi cally their sharp emission peaks. This, along with the fact that they don't photobleach and are relatively nontoxic, make them ideal for biological probes. If the ligand in the complex can be functionalized to couple with an antibody, the complex should then be able to follow the antibody wherever it goes, for example, to a cancerous tumor, and the probes would then aggregate in the area, causing localized luminescence, aiding in early detection of cancer.

This thesis reports the synthesis of a 42-nuclear lanthanide nano-ring: likely the highest nuclearity lanthanide complex ever produced. This complex, referred to as Ln 42, is produced by reacting an ortho-vanillin based ligand with lanthanide acetate, the suitable lanthanides being gadolinium, terbium, dysprosium, and holmium. The complex self-assembles, interestingly, fi rst hydrolyzing the ligand such that the only portion that remains in the final complex is deprotonated ortho-vanillin. Acetate and hydroxyl groups also remain in the final complex, in addition to the lanthanide centers. The structure in the crystalline solid state was determined using single crystal X-ray diffraction.