Molecules are highly social: they recognize one another and form bonds with those they are attracted to and repel those they are not. Some molecules establish strong bonds, while others form weak, transient associations. These interactions are ubiquitous in Nature and are integral to life. For at the basis of many biological processes lies the ability of molecules to recognize and respond to one another. Molecular chaperonins and G-protein-coupled receptors, for example, rely on the reversible binding of molecules and proteins to guide crucial cellular functions ranging from protein folding to signal transduction. To achieve these tasks, the proteins assemble to form binding sites that reversibly and selectively bind guests through weak, intermolecular interactions known as supramolecular interactions. These supramolecular interactions render proteins allosteric, which enables them to adapt their structure and activity in response to changing chemical environments and, as a result, facilitate complex chemical processes. Nature’s ability to orchestrate such complex chemistries, has inspired chemists to develop synthetic enzyme mimics capable of allosteric regulation. Coordination chemistry has emerged as a powerful means to design inorganic constructs that exploit supramolecular interactions. This thesis describes the design and synthesis of bioinspired, stimuli-responsive coordination constructs, assembled via the Weak-Link approach (WLA). The WLA represents one of the few sets of fundamental reactions in inorganic chemistry that allow one to synthesize spatially defined, stimuli-responsive, and multi-component frameworks in high to quantitative yields and with remarkable functional group tolerance. The WLA enables access to distinctly different structural states via small-molecule reactions at a metal node, which affect the coordination of hemilabile ligands. The generality and applications of this approach are demonstrated in Chapter 1. In Chapter 2, an allosterically regulated macrocycle reminiscent of a protein binding pocket, is designed and characterized. As described in Chapter 3, this system can access four distinct states and may be used in the construction of sophisticated stimuli-responsive sensors and receptors. In Chapters 4 and 5, we show that the principles of the WLA may be extended to the design and synthesis of stimuli-responsive materials. Finally, in Chapter 6, new types of stimuli-responsive WLA systems are explored.

Creator

• d'Aquino, Andrea

DOI

• https://doi.org/10.21985/n2-3q0v-vx21

Subject

• Chemistry

Language

• en

Alternate Identifier

• http://dissertations.umi.com/northwestern:14962
• etdadmin_upload_712493

Keyword

• Supramolecular chemistry
• Weak-Link Approach
• Organometallic chemistry
• Coordination chemistry

Date created

• 2019-01-01

Resource type

• Dissertation

Rights statement

• In Copyright