A Solid-Solution Approach to Multivariate Metal-Organic Frameworks and Their Interactions with Light

This thesis studies the application of a substitutional solid solution (SSS) approach to multivariate metal organic frameworks (MTV MOFs) with a focus on preparing functional organic-inorganic materials. MOFs are a class of crystalline coordination polymers that form 3-dimensional structures with pores. The empty space in the unit cell of these materials allows for the incorporation of functionalized links and leads to a sub-class known as MTV MOFs, where multiple links of varied functionality are incorporated into the same material. MTV MOFs function similarly to the inorganic concept of SSS were a solute atom is dissolved inside a matrix, allowing for a high degree of control over the material\u27s properties, as it is done in materials for lasers and blue LEDs. The application of an SSS approach to MTV MOFs was chosen to allow the preparation of highly tunable solid-state materials, were the properties can be controlled via the preparation and quantity of the organic link incorporated into the MTV MOF. To study this approach, emission was utilized as a means to observe possible solution-like properties in the solid state. The first topic of this work describes the preparation of molecular links for a multifluorophore system. These links were then incorporated into a MTV MOF, in the next chapter, where the emission was studied as a function of solid-state concentration. Next, a series of MOFs were prepared containing an aggregate forming fluorescent dye, where the structure of the MOF was utilized to study aggregation as a function of emission. The last chapter focuses on preliminary results on strategies to prepare thin films of the previously prepared MTV MOFs. This thesis demonstrates the ability to separate the structure of a material from its properties and observe tunable traits based solely on the concentration of the organic molecules incorporated into the MTV MOF