The human body uses large, complex molecules such as enzymes (a type of protein) to control many cellular processes. Chemists strive to mimic the complexity of these biological structures with artificial analogs, but these mimics cannot approach the complexity of natural enzymes. Self-assembly is a powerful approach to create large, complex molecules without the challenge of complex step-by-step synthesis. This process is similar to molecular-level Lego, whereby individual pieces can be simply put together to make a larger, more complex structure. In this research project, Prof. Hooley aims to develop self-assembly approaches to creating new chemical structures that act in a manner similar to enzymes and to explore the potential applications of these structures in catalysis. This project provides interdisciplinary research training to graduate students and opportunities to underrepresented undergraduates for intellectual and creative development. Educational innovations are integrated with research to encourage undergraduates and underrepresented minorities to pursue careers in science and to improve the chemistry curriculum at UC Riverside with a focus on increasing retention of students in STEM fields.
Self-assembled cage complexes can display novel material and sensing properties, but simple molecular polyhedra have limits in their functional applications. Prof. Hooley's research group seeks to remedy this by creating new functional synthetic receptors via metal-ligand based self-assembly. This project focuses on three specific areas: 1) the application of internal functions of ligands to control (via secondary weak interactions) the self-assembly process, including self-sorting and the control of stoichiometry and stereochemistry of cage complexes; 2) post-assembly modifications of internal functional groups to alter reactivity and to allow controlled, reversible structural switching between different polyhedral geometries and trapping of cage complexes; and 3) the application of these complexes as biomimetic catalysts in tandem, orthogonal catalysis. An important objective in this area is to demonstrate that the sequestration of acidic and basic functions in cage interiors allows normally incompatible reactions to be performed in a single pot.
