Name(s) of Faculty Adviser/Mentor

Stephen Holmes

Document Type



There has been emerging worldwide research dedicated to finding molecular complexes suitable for molecule-based high-density information storage via intramolecular electron transfer. A known cyanoferrate switchable material, Prussian Blue, has inspired research efforts of Holmes et al. to create families of heterometallic Prussian Blue derivatives that display optical and magnetic behavioral transitions with the variation of light and temperature. The task for my undergraduate research project is synthesizing massive switchable molecular clusters containing cyano-bridged Fe and Mn units. During the process, Marcus-Hush theory of electron transfer was an important consideration during the synthesis of tri- and tetranuclear complexes with varying redox potentials and ligand environments to impact the movement of electrons in the metal centers. Using a method known as “self assembly” with the building blocks of [(TpR)Fe(CN)3]- (TpR = poly (pyrazolyl)borates), Manganese cation complexes, along with the combinations of 2 different bidentate ligands and 2 choices of counteranions I have produced a closely related family of novel cyanometalate complexes. When looking for electron transfer, I found that the compounds have altogether failed according to variable temperature IR spectra collected from 77 K to 300 K. I present my observed trends and further plans and predictions of the synthetic design,; this includes tuning the electron density of the metal centers and how to encourage electron transfer using electrophiles bonded to the cyanides within the structure to forcefully pull the electrons through the cyanide bridges. Ultimately, my studies have shown each unique complex helps us understand the variety of factors and challenges that relate to structure-property relationships in the manufacture of electron transfer and spin crossover complexes.

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