Date of Award


Degree Type


Degree Name



Chemistry and Biochemistry

First Advisor

Loeb, Stephen


Chemistry, Metal-Organic Frameworks, Molecular machines, Reticular, Rotaxane, Supramolecular




The work herein, describes the placement of mechanically interlocked molecules (MIMs) into ordered, crystalline metal-organic frameworks (MOFs) to create metal-organic rotaxane frameworks (MORFs). This placement is done through the use of the concepts of reticular synthesis, to create predictable materials based on prior known building blocks and topological nets in order to achieve robust dynamics. The concepts of MIMs, nets, reticular synthesis, robust dynamics are all discussed in detail in Chapter 1. Also outlined in Chapter 1 are six design criteria that act as a blueprint for the creation of robust dynamics using the tenants of reticular synthesis. Chapter 2 shows the targeting of nbo derived topological nets for incorporating a T-shaped [2]rotaxane linker. The targeting of this net produced three MOFs of UWCM-CH3 and the two phases of α/β-UWDM-CF3 (University of Windsor Crystalline Material). Topological analysis of the nets show that the nbo derived fof net was produced by UWCM-CH3 and α-UWCM-CF3. Also reported is the first instance of the newly named loz net of β-UWCM-CF3. Chapter 3 is an evolution of the T-shaped linker design for the targeting of lvt nets. This endeavour resulted in the isoreticular lil nets of UWCM-10 and the MIM containing UWDM-10 (University of Windsor Dynamic Material). Through the use of variable temperature 2H solid-state nuclear magnetic resonance spectroscopy (SSNMR), the rotational motion of the mechanically bound wheel of the [2]rotaxane was characterised. Chapter 4 uses a linear T-shaped linker design to target the edge-transitive pcu net resulting in the isoreticular MOF and MORFs, UWCM-11 and UWDM-11. The rotational dynamics of UWDM-11 were probed using VT 2H SSNMR. Chapter 5 uses the same linear T-shaped [2]rotaxane linker for incorporation into the edge-transitive net of fcu producing UWDM-12. The Zr MOF was targeted for the high chemical stability of the secondary building unit (SBU) allowing for acid/base chemistry on the benzimidazole/benzimidazolium axle of the [2]rotaxane. This produced both UWDM-12[Neutral] and UWDM-12[Protonated] that were shown through VT 2H SSNMR to have a qualitative effect on the rotational dynamics of the mechanically bound wheel inside the framework – a first for the UWDM series. Chapter 6 evaluates the six design objectives, and debates their practicality in the pursuit of creating robust dynamics by using reticular synthesis.