Date of Award

Fall 2022

Document Type

Open Access Dissertation


Chemistry and Biochemistry

First Advisor

John J. Lavigne


In past decades, research in self-assembling supramolecular frameworks have been produced with vast surface area, inherent from their porous nature. Predesigning monomers in a reticular manner allows a framework’s structure to be known before self-assembly occurs. This is very helpful since high porosity is sought after for many purposes such as hosting guests within the framework, post-synthetic modifications, sensing and detection, selective catalysis, semiconduction, etc. Methods of design usually focus on forming intrinsic porosity and unfortunately, sometimes the network formed is not as expected and porosity is lost.

In Chapter 1, we discuss novel ways of network formation, their potential pitfalls from reticular design, and the idea of using recyclable materials to form extrinsically porous supramolecular networks. Also included is the introduction of our new approach to solving the issues that arise in reticular design.

Chapters 2, 3, 4 consists of extrinsically porous and robust single crystalline networks formed from the same recyclable diboronate ester and pyridyl linker. Chapter 2 focuses on a coordinated polymer network in which post-synthetic modification is performed using single crystal to single crystal (SCSC) transitions which replace the guests within the host and change the framework’s structure. Also included is an investigation of enthalpic binding strength to answer the reversibility seen. Chapter 3 discusses using these materials to form frameworks having different characteristics and structures arising from solvent driven origins. Chapter 4 also uses these materials in which a crystalline network forms from interdigitating macrocycles. This framework is capable of irreversible SCSC transitions that must occur in a stepwise manner which creates products that cannot be formed with typical procedures.

Chapter 5 presents a new approach to synthesize highly porous supramolecular covalent organic frameworks that are fully conjugated in every direction to have semiconductor potential. This effort for multiscale porosity uses a three-dimensional intrinsically porous bicyclic cage starting material that can dynamically bond to form azodioxide bridges capable of extending electron communication in every direction and expected to be in single crystal form. This approach also comes with guidelines to force the product to follow the reticular design while blocking chances of interpenetration which counters the efforts given for high porosity.

Chapter 6 discusses future directions in research for future graduate student and undergraduate researchers.


© 2022, Steven A Sloope

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